Process for producing amide compound

ABSTRACT

There is provided a process for producing an amide compound having an excellent harmful arthropod-controlling activity and represented by the formula (3): 
     
       
         
         
             
             
         
       
     
     wherein R 1 , R 2  and R 3  independently represent a C1-C6 alkyl group optionally substituted with at least one halogen atom etc., R 4 , R 5 , R 6  and R 7  independently represent a halogen atom etc.

TECHNICAL FIELD

The present invention relates to a novel process for producing an amidecompound, intermediated compounds thereof, and the like.

BACKGROUND ART

To date, many compounds for controlling harmful arthropods have beendeveloped and come into practical use. WO 01/70671 and WO 03/015518disclose certain amide compounds having an arthropod-controllingactivity.

DISCLOSURE OF THE INVENTION

The present inventors studied intensively a process for producing anamide compound having an excellent controlling activity on harmfularthropods represented by the following formula (3):

wherein R¹ represents a C1-C6 alkyl group optionally substituted with atleast one halogen atom, R² represents a hydrogen atom, or a C1-C6 alkylgroup optionally substituted with at least one halogen atom, R³represents a C1-C6 alkyl group optionally substituted with at least onehalogen atom, a C3-C6 alkoxyalkyl group optionally substituted with atleast one halogen atom, a C3-C6 alkenyl group optionally substitutedwith at least one halogen atom, or a C3-C6 alkynyl group optionallysubstituted with at least one halogen atom, R⁴ represents a halogenatom, or a C1-C6 alkyl group optionally substituted with at least onehalogen atom, and R⁵ represents a hydrogen atom, a halogen atom, a cyanogroup, or a C1-C6 alkyl group optionally substituted with at least onehalogen atom, R⁶ represents a hydrogen atom, a halogen atom, a cyanogroup, a C1-C6 alkyl group optionally substituted with at least onehalogen atom, a C1-C6 alkoxy group optionally substituted with at leastone halogen atom, a C1-C6 alkylthio group optionally substituted with atleast one halogen atom, a C1-C6 alkylsulfinyl group optionallysubstituted with at least one halogen atom, or a C1-C6 alkylsulfonylgroup optionally substituted with at least one halogen atom, and R⁷represents a halogen atom, or a C1-C6 alkyl group optionally substitutedwith at least one halogen atom and, as a result, completed the presentinvention. The present invention provides:[1] a process for producing an amide compound represented by the formula(3):

wherein R¹ represents a C1-C6 alkyl group optionally substituted with atleast one halogen atom, R² represents a hydrogen atom, or a C1-C6 alkylgroup optionally substituted with at least one halogen atom, R³represents a C1-C6 alkyl group optionally substituted with at least onehalogen atom, a C3-C6 alkoxyalkyl group optionally substituted with atleast one halogen atom, a C3-C6 alkenyl group optionally substitutedwith at least one halogen atom, or a C3-C6 alkynyl group optionallysubstituted with at least one halogen atom, R⁴ represents a halogenatom, or a C1-C6 alkyl group optionally substituted with at least onehalogen atom, and R⁵ represents a hydrogen atom, a halogen atom, a cyanogroup, or a C1-C6 alkyl group optionally substituted with at least onehalogen atom, R⁶ represents a hydrogen atom, a halogen atom, a cyanogroup, a C1-C6 alkyl group optionally substituted with at least onehalogen atom, a C1-C6 alkoxy group optionally substituted with at leastone halogen atom, a C1-C6 alkylthio group optionally substituted with atleast one halogen atom, a C1-C6 alkylsulfinyl group optionallysubstituted with at least one halogen atom, or a C1-C6 alkylsulfonylgroup optionally substituted with at least one halogen atom, and R⁷represents a halogen atom, or a C1-C6 alkyl group optionally substitutedwith at least one halogen atom (hereinafter referred to as the compound(3)), which comprises reacting an aniline compound represented by theformula (1):

wherein R¹, R², R³, R⁴ and R⁵ are as defined above (hereinafter referredto as the compound (1)), with an aldehyde compound represented by theformula (2):

wherein R⁶ and R⁷ are as defined above (hereinafter referred to as thecompound (2)), in a solvent in the presence of a quinone compound;[2] the process according to the above [1], wherein the quinone compoundis a compound selected from the group consisting of2,3-dichloro-5,6-dicyano-1,4-benzoquinone, tetrachloro-1,2-benzoquinone,and tetrachloro-1,4-benzoquinone;[3] an aniline compound represented by the formula (1):

wherein R¹ represents a C1-C6 alkyl group optionally substituted with atleast one halogen atom, R² represents a hydrogen atom, or a C1-C6 alkylgroup optionally substituted with at least one halogen atom, R³represents a C1-C6 alkyl group optionally substituted with at least onehalogen atom, a C3-C6 alkoxyalkyl group optionally substituted with atleast one halogen atom, a C3-C6 alkenyl group optionally substitutedwith at least one halogen atom, or a C3-C6 alkynyl group optionallysubstituted with at least one halogen atom, R⁴ represents a halogenatom, or a C1-C6 alkyl group optionally substituted with at least onehalogen atom, and R⁵ represents a hydrogen atom, a halogen atom, a cyanogroup, or a C1-C6 alkyl group optionally substituted with at least onehalogen atom;[4] the aniline compound according to the above [3], wherein R¹represents a methyl group or an ethyl group, and R² represents ahydrogen atom, a methyl group or an ethyl group;[5] the aniline compound according to the above [4], wherein R¹ and R²each represent a methyl group;[6] the aniline compound according to the above [4], wherein R¹represents a methyl group and R² represents a hydrogen atom;[7] the aniline compound according to the above [4], wherein R¹represents an ethyl group and R² represents a hydrogen atom;[8] an aldehyde compound represented by the formula (2):

wherein R⁶ represents a hydrogen atom, a halogen atom, a cyano group, aC1-C6 alkyl group optionally substituted with at least one halogen atom,a C1-C6 alkoxy group optionally substituted with at least one halogenatom, a C1-C6 alkylthio group optionally substituted with at least onehalogen atom, a C1-C6 alkylsulfinyl group optionally substituted with atleast one halogen atom, or a C1-C6 alkylsulfonyl group optionallysubstituted with at least one halogen atom, and R⁷ represents a halogenatom, or a C1-C6 alkyl group optionally substituted with at least onehalogen atom;[9] the aldehyde compound according to the above [8], wherein R⁶represents a halogen atom or a C1-C6 alkyl group optionally substitutedwith at least one halogen atom;[10] the aldehyde compound according to the above [9], wherein R⁶represents a halogen atom or a trifluoromethyl group;[11] the aldehyde compound according to the above [10], wherein R⁶represents a chlorine atom or a trifluoromethyl group, and R⁷ representsa chlorine atom;[12] an amide compound represented by the formula (3a):

wherein R³ represents a C1-C6 alkyl group optionally substituted with atleast one halogen atom, a C3-C6 alkoxyalkyl group optionally substitutedwith at least one halogen atom, a C3-C6 alkenyl group optionallysubstituted with at least one halogen atom, or a C3-C6 alkynyl groupoptionally substituted with at least one halogen atom, R⁴ represents ahalogen atom, or a C1-C6 alkyl group optionally substituted with atleast one halogen atom, and R⁵ represents a hydrogen atom, a halogenatom, a cyano group, or a C1-C6 alkyl group optionally substituted withat least one halogen atom, R⁶ represents a hydrogen atom, a halogenatom, a cyano group, a C1-C6 alkyl group optionally substituted with atleast one halogen atom, a C1-C6 alkoxy group optionally substituted withat least one halogen atom, a C1-C6 alkylthio group optionallysubstituted with at least one halogen atom, a C1-C6 alkylsulfinyl groupoptionally substituted with at least one halogen atom, or a C1-C6alkylsulfonyl group optionally substituted with at least one halogenatom, and R⁷ represents a halogen atom, or a C1-C6 alkyl groupoptionally substituted with at least one halogen atom;[13] the amide compound according to the above [12], wherein R³represents a methyl group, R⁴ represents a chlorine atom, a bromine atomor a methyl group, R⁵ represents a chlorine atom, a bromine atom or acyano group, R⁶ represents a chlorine atom, a bromine atom or atrifluoromethyl group, and R⁷ represents a chlorine atom;[14] a pesticidal composition comprising the amide compound according tothe above [12] or [13] as an active ingredient;[15] use of the amide compound according to the above [12] or [13] as anactive ingredient for a pesticidal composition;[16] a method of controlling a harmful arthropod which comprisesapplying the amide compound according to the above [12] or [13] directlyto the harmful arthropod, or to a place where the harmful arthropodinhabits;[17] use of the amide compound according to the above [12] or [13] formanufacturing a pesticidal composition;[18] a compound represented by the formula (17):

wherein R⁶ represents a hydrogen atom, a halogen atom, a cyano group, aC1-C6 alkyl group optionally substituted with at least one halogen atom,a C1-C6 alkoxy group optionally substituted with at least one halogenatom, a C1-C6 alkylthio group optionally substituted with at least onehalogen atom, a C1-C6 alkylsulfinyl group optionally substituted with atleast one halogen atom, or a C1-C6 alkylsulfonyl group optionallysubstituted with at least one halogen atom, and R⁷ represents a halogenatom, or a C1-C6 alkyl group optionally substituted with at least onehalogen atom, and R^(c) represents a C1-C4 alkyl group;[19] the compound according to the above [18], wherein R⁶ represents ahalogen atom or a C1-C6 alkyl group optionally substituted with at leastone halogen atom; and the like.

According to the process of the present invention, the compound (3)having an excellent controlling activity on harmful arthropods can beproduced.

BEST MODE FOR CARRYING OUT THE INVENTION

In the process of the present invention, usually 0.5 to 2 mol of thecompound (2) is used per 1 mol of the compound (1). The used amounts ofthe compound (1) and the compound (2) may be varied depending on thereaction situation.

The reaction of the compound (1) with the compound (2) is performed inthe presence of a quinone compound. The quinone compound as used hereinrefers to a compound obtained by replacing two of CH atomic groups in anaromatic compound with CO atomic groups, and then moving double bonds soas to form quinoid structure. Quinone compounds are roughly classifiedinto p-quinone compounds and o-quinone compounds on the basis of quinoidstructure, and p-quinone compounds and o-quinone compounds have thefollowing basic structure (a) and (b) respectively.

Examples of the quinone compound include p-quinone compounds such as2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ),tetrachloro-1,4-benzoquinone (p-chloranil) and the like, and o-quinonecompounds such as tetrachloro-1,2-benzoquinone (o-chloranil) and thelike. In the process of the present invention, p-chloranil oro-chloranil is preferably used.

The amount of the quinone compound used in the reaction is preferably 1to 2 mol per 1 mol of the compound (2), and the used amount may bevaried depending on the reaction situation. Alternatively, the reactioncan be performed using less than 1 mol, that is, a catalytic amount ofthe quinone compound and not less than 1 mol of a co-oxidizing agent per1 mol of the compound (2). In the case of using a catalytic amount ofthe quinone compound, examples of the co-oxidizing agent which can beused include oxygen, hydrogen peroxide, alkyl hydroperoxide,percarboxylic acid, sodium hypochlorite and the like.

The reaction is performed in a solvent. Examples of the solvent whichcan be used include ether solvents such as 1,4-dioxiane, diethyl ether,tetrahydrofuran, methyl tert-butyl ether and the like; halogenatedhydrocarbon solvents such as dichloromethane, chloroform, carbontetrachloride, 1,2-dichloroethane, chlorobenzene and the like;hydrocarbon solvents such as hexane, heptane, toluene, benzene, xyleneand the like; nitrile solvents such as acetonitrile and the like; amidesolvents such as N,N-dimethylformamide and the like; nitrogen-containingcyclic compound solvents such as N-methylpyrrolidone,1,3-dimethyl-2-imidazolidinone and the like; aprotic solvents, forexample, sulfoxide solvents such as dimethyl sulfoxide; carboxylic acidsolvents such as acetic acid and the like; ketone solvents such asacetone, isobutyl methyl ketone and the like; ester solvents such asethyl acetate and the like; alcohol solvents such as 2-propanol,tert-butyl alcohol and the like; and water. Two or more of theabove-mentioned solvents may be used as a mixture, and the reaction maybe performed in a single-phase system or a two-phase system.

The temperature of the reaction is usually in a range of 0 to 150° C.,and the reaction time is usually in a range of instant to 72 hours.

In the reaction, an acid may be present as necessary. Examples of theacid which can be used include mineral acids such as hydrochloric acid,sulfuric acid, nitric acid, phosphoric acid, perchloric acid and thelike; carboxylic acids such as acetic acid, benzoic acid and the like;sulfonic acids such as methanesulfonic acid, benzenesulfonic acid,p-toluenesulfonic acid and the like; boron compounds such as borontrifluoride and the like; aluminum compounds such as aluminum(III)chloride, aluminum(III) isopropoxide and the like; titanium compoundssuch as titanium(IV) tetrachloride, titanium(IV) isopropoxide and thelike; zinc compounds such as zinc(II) chloride; iron compounds such asiron(III) chloride and the like.

In the case of using an acid in the reaction, the amount of the acidused is usually 0.001 to 1 mol per 1 mol of the compound (2), and theused amount may be varied depending on the reaction situation.

After completion of the reaction, the reaction mixture is poured intowater and then extracted with an organic solvent, or the reactionmixture is poured into water and formed precipitates are collected byfiltration, thereby the compound (3) can be isolated. The isolatedcompound (3) can be further purified by recrystallization,chromatography or the like.

Then, a process for producing the compound (1) and the compound (2) usedin the process of the present invention will be explained.

The compound (1) can be produced according to Scheme (1).

wherein, R¹, R², R³, R⁴ and R⁵ are as defined above.

[Compound (4)→Compound (1)]

The amount of the compound (7) used is usually 1 mol per 1 mol ofcompound (4).

The reaction is usually performed in the presence of a solvent. Examplesof the solvent include ethers such as 1,4-dioxane, diethyl ether,tetrahydrofuran, methyl tert-butyl ether and the like, halogenatedhydrocarbons such as dichloromethane, chloroform, carbon tetrachloride,1,2-dichloroethane, chlorobenzene and the like, hydrocarbons such astoluene, benzene, xylene and the like, nitriles such as acetonitrile andthe like, aprotic polar solvents such as N,N-dimethylformamide,N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone, dimethyl sulfoxideand the like, alcohols such as methanol, ethanol, isopropyl alcohol andthe like, and a mixture thereof.

Among the compounds (1), a compound represented by the formula (1-i) canbe produced according to Scheme (2).

wherein, R¹² represents a C1-C6 alkyl group optionally substituted withat least one halogen atom, L¹ represents a leaving group (e.g. a halogenatom, a methanesulfonyloxy group or a p-toluenesulfonyloxy group), andR³, R⁴ and R⁵ are as defined above.[Compound (4)→Compound (5-i)]

The amount of the compound (7-i) used is usually 1 mol per 1 mol of thecompound (4).

The reaction is usually performed in a solvent. Examples of the solventinclude ethers such as 1,4-dioxane, diethyl ether, tetrahydrofuran,methyl tert-butyl ether and the like, halogenated hydrocarbons such asdichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane,chlorobenzene and the like, hydrocarbons such as toluene, benzene,xylene and the like, nitriles such as acetonitrile and the like, aproticpolar solvents such as N,N-dimethylformamide, N-methylpyrrolidone,1,3-dimethyl-2-imidazolidinone, dimethyl sulfoxide and the like,alcohols such as methanol, ethanol, isopropyl alcohol and the like, anda mixture thereof.

[Compound (5-i)→Compound (1-i)]

1) Protection

The amino group (—NH₂) on the benzene ring of the compound (5-i) can beprotected with a suitable protecting group (e.g. N-benzylidene group,N-(1-methyl)ethylidene group) described in Greene's Protective Groups inOrganic Synthesis (WILEY) etc., if necessary.

2) Base+R¹²-L¹ (9-i) or (R¹²O)₂SO₂ (10-i)

The amount of the compound (9-i) or the compound (10-i) used is usually2 mol per 1 mol of the compound (5-i) or a derivative thereof in whichthe amino group is protected. Examples of a base used in the reactioninclude metal carbonates such as potassium carbonate, sodium carbonateand the like, metal hydroxides such as lithium hydroxide, sodiumhydroxide, potassium hydroxide and the like, and metal hydrides such assodium hydride and the like.

3) Deprotection

The compound (1-i) in which the amino group is protected can bedeprotected under known conditions.

Among the compounds (1), a compound represented by the formula (1-ii)can be produced according to Scheme (3).

wherein R¹, R³, R⁴ and R⁵ are as defined above.[Compound (4)→Compound (6-ii)]

The amount of the compound (8-ii) used is usually 1 mol per 1 mol of thecompound (4).

The reaction is usually performed in a solvent. Examples of the solventinclude ethers such as 1,4-dioxane, diethyl ether, tetrahydrofuran,methyl tert-butyl ether and the like, halogenated hydrocarbons such asdichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane,chlorobenzene and the like, hydrocarbons such as toluene, benzene,xylene and the like, nitriles such as acetonitrile and the like, aproticpolar solvents such as N,N-dimethylformamide, N-methylpyrrolidone,1,3-dimethyl-2-imidazolidinone, dimethyl sulfoxide and the like,alcohols such as methanol, ethanol, isopropyl alcohol and the like, anda mixture thereof.

[Compound (6-ii)→Compound (1-ii)]

1) Protection

The amino group (—NH₂) on the benzene ring of the compound (6-ii) can beprotected with a suitable protecting group (e.g. N-benzylidene group,N-(1-methyl)ethylidene group) described in Greene's Protective Groups inOrganic Synthesis (WILEY) etc., if necessary.

2) Base+Cl—CO₂R³ (11)

The amount of the compound (11) used is usually 1 mol per 1 mol of thecompound (6-ii) or a derivative thereof in which the amino group isprotected. Examples of a base used in the reaction include metalcarbonates such as sodium carbonate, potassium carbonate, cesiumcarbonate and the like, metal hydroxides such as lithium hydroxide,sodium hydroxide, potassium hydroxide and the like, and metal hydridessuch as sodium hydride and the like.

3) Deprotection

The compound (1-ii) in which the amino group is protected can bedeprotected under known conditions.

Among the compounds (1), a compound represented by the formula (1-iii)can be produced according to Scheme (4).

wherein, R¹⁰ and R²⁰ represent a C1-C6 alkyl group optionallysubstituted with at least one halogen atom, and R³, R⁴, R⁵ and L¹ are asdefined above.[Compound (4)→Compound (5-ii)]

The amount of the compound (7-iv) used is usually 1 mol per 1 mol of thecompound (4).

The reaction is usually performed in a solvent. Examples of the solventinclude ethers such as 1,4-dioxane, diethyl ether, tetrahydrofuran,methyl tert-butyl ether and the like, halogenated hydrocarbons such asdichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane,chlorobenzene and the like, hydrocarbons such as toluene, benzene,xylene and the like, nitriles such as acetonitrile and the like, aproticpolar solvents such as N,N-dimethylformamide, N-methylpyrrolidone,1,3-dimethyl-2-imidazolidinone, dimethyl sulfoxide and the like,alcohols such as methanol, ethanol, isopropyl alcohol and the like, anda mixture thereof.

[Compound (5-ii)→Compound (1-iii)]

1) Protection

The amino group (—NH₂) on the benzene ring of the compound (5-ii) can beprotected with a suitable protecting group (e.g. N-benzylidene group,N-(1-methyl)ethylidene group) described in Greene's Protective Groups inOrganic Synthesis (WILEY) etc., if necessary.

2) Base+R¹⁰-L¹ (9-iii) or (R¹⁰O)₂SO₂ (10-iii)

The amount of the compound (9-iii) or the compound (10-iii) used isusually 1 mol per 1 mol of the compound (5-ii) or a derivative thereofin which the amino group is protected. Examples of a base used in thereaction include metal carbonates such as sodium carbonate, potassiumcarbonate, cesium carbonate and the like, metal hydroxides such aslithium hydroxide, sodium hydroxide, potassium hydroxide and the like,and metal hydrides such as sodium hydride and the like.

3) Deprotection

The compound (1-iii) in which the amino group is protected can bedeprotected under known conditions.

The compound (4) is a known compound, or can be produced according tothe following Scheme (5).

wherein R⁴ and R⁵ are as defined above.

The compounds (7-i), (7-ii), (7-iii) and (7-iv) are known compounds, orcan be produced according to the following Scheme (6).

wherein, R⁸ represents a C1-C6 alkyl group optionally substituted withat least one halogen atom, and R³ and R¹² are as defined above.

The compounds (8-i), (8-ii) and (8-iii) are known compounds, or can beproduced from known compounds according to known methods (see, forexample, Organic Functional Group Preparations, 2nd edition, Vol. 1,chapter 14, p. 434-465, Stanley R. Sandler, Wolf Karo).

Among the compounds (7), a compound represented by the formula (7-v) canbe produced according to Scheme (7).

wherein R^(b) represents a C1-C5 alkyl group optionally substituted withat least one halogen atom, and R³ is as defined above.[Compound (7-i)→Compound (16)]

The amount of R^(b)—CHO used is usually 1 to 2 mol per 1 mol of thecompound (7-i).

The reaction is usually performed in a solvent. Examples of the solventinclude ethers such as 1,4-dioxane, diethyl ether, tetrahydrofuran,methyl tert-butyl ether and the like, halogenated hydrocarbons such asdichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane,chlorobenzene and the like, hydrocarbons such as toluene, benzene,xylene and the like, nitriles such as acetonitrile and the like, aproticpolar solvents such as N,N-dimethylformamide, N-methylpyrrolidone,1,3-dimethyl-2-imidazolidinone, dimethyl sulfoxide and the like,alcohols such as methanol, ethanol, isopropyl alcohol and the like, anda mixture thereof.

[Compound (16)→Compound (7-v)]

The amount of sodium borohydride used is usually 0.25 to 2 mol per 1 molof the compound (16).

The reaction is usually performed in a solvent. Examples of the solventinclude ethers such as 1,4-dioxane, diethyl ether, tetrahydrofuran,methyl tert-butyl ether and the like, halogenated hydrocarbons such asdichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane,chlorobenzene and the like, hydrocarbons such as toluene, benzene,xylene and the like, nitriles such as acetonitrile and the like, aproticpolar solvents such as N,N-dimethylformamide, N-methylpyrrolidone,1,3-dimethyl-2-imidazolidinone, dimethyl sulfoxide and the like,alcohols such as methanol, ethanol, isopropyl alcohol and the like, anda mixture thereof.

The compound (2) can be produced according to a method, for example,shown in the following Scheme (8).

wherein, L² represents a leaving group (e.g. halogen atom,methylsulfonyl group etc.), L³ represents a leaving group (e.g. methoxygroup, ethoxy group, N,N-dimethylamino group, 1-imidazolyl group etc.),and R⁶ and R⁷ are as defined above.

[Compound (13)→Compound (2)] 1) Base+3-(R⁶)-Substituted-1H-Pyrazole

The amount of the 3-(R⁶)-substituted-1H-pyrazole used is usually 1 molper 1 mol of the compound (13). Examples of a base used in the reactioninclude metal carbonates such as sodium carbonate, potassium carbonate,cesium carbonate and the like, metal hydroxides such as lithiumhydroxide, sodium hydroxide, potassium hydroxide and the like, and metalhydrides such as sodium hydride and the like.

The reaction is usually performed in a solvent. Examples of the solventinclude ethers such as 1,4-dioxane, diethyl ether, tetrahydrofuran,methyl tert-butyl ether and the like, nitriles such as acetonitrile andthe like, aprotic polar solvents such as N,N-dimethylformamide,N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone, dimethyl sulfoxideand the like, and a mixture thereof.

2) LDA, then HC(═O)-L³ (15)

The amount of LDA (lithium diisopropylamide) used is usually 1 mol andthe amount of the compound (15) used is usually 1 mol, per 1 mol of2-[3-(R⁶)-substituted-1H-pyrazol-1-yl]-3-(R⁷)-substituted pyridine.

The reaction is usually performed in a solvent. Examples of the solventinclude ethers such as 1,4-dioxane, diethyl ether, tetrahydrofuran,methyl tert-butyl ether and the like, hydrocarbons such as toluene,benzene, xylene and the like, and a mixture thereof.

The compound (13) is a known compound, or can be produced from a knowncompound according to a known method.

The compound (2) can also be produced according to a method, forexample, shown in the following Scheme (9).

wherein R^(c) represents a C1-C4 alkyl group, and R⁶ and R⁷ are asdefined above.

Examples of an oxidizing agent used in the reaction include persulfatessuch as sodium persulfate, potassium persulfate, ammonium persulfate andthe like. The amount of the oxidizing agent used is usually 1 to 2 molper 1 mol of the compound (17).

The reaction is usually performed in a solvent. Examples of the solventinclude nitriles such as acetonitrile and the like, water and a mixturethereof.

Among the compounds (17), a compound represented by the formula (17-i)can be produced, for example, according to Scheme (10).

wherein R^(d) represents a methyl group, a phenyl group or a p-tolylgroup, L⁴ represents a chlorine atom or a bromine atom, X¹ represents ahalogen atom, and R^(c) and R⁷ are as defined above.

[Compound (18)→Compound (19)]

Examples of H-L⁴ include hydrogen chloride and hydrogen bromide.

The reaction is usually performed in a solvent. Examples of the solventinclude ethers such as 1,4-dioxane, diethyl ether, methyl tert-butylether and the like, halogenated hydrocarbons such as dichloromethane,chloroform, carbon tetrachloride, 1,2-dichloroethane, chlorobenzene andthe like, hydrocarbons such as toluene, benzene, xylene and the like,and a mixture thereof.

[Compound (19)→Compound (20)]

Examples of a chlorinating agent used in the reaction include oxalyldichloride, thionyl chloride and the like. The amount of thechlorinating agent used is usually 1 to 10 mol per 1 mol of the compound(19).

The reaction is performed under a solventless condition or in a solvent.Examples of the solvent include ethers such as 1,4-dioxane, diethylether, methyl tert-butyl ether and the like, halogenated hydrocarbonssuch as dichloromethane, chloroform, carbon tetrachloride,1,2-dichloroethane, chlorobenzene and the like, hydrocarbons such astoluene, benzene, xylene and the like, nitriles such as acetonitrile andthe like, and a mixture thereof.

[Compound (20)→Compound (22)]

The reaction is usually performed in a solvent. Examples of the solventinclude ethers such as 1,4-dioxane, diethyl ether, tetrahydrofuran,methyl tert-butyl ether and the like, halogenated hydrocarbons such asdichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane,chlorobenzene and the like, hydrocarbons such as toluene, benzene,xylene and the like, nitriles such as acetonitrile and the like, aproticpolar solvents such as N,N-dimethylformamide, N-methylpyrrolidone,1,3-dimethyl-2-imidazolidinone, dimethyl sulfoxide and the like, and amixture thereof.

The amount of the compound (21) used in the reaction is usually 1 molper 1 mol of the compound (20).

The reaction is performed in the presence of a base, as necessary.Example of the base include nitrogen-containing heterocyclic compoundssuch as pyridine, picoline, 2,6-lutidine1,8-diazabicyclo[5.4.0]7-undecene (DBU), 1,5-diazabicyclo[4.3.0]5-nonene(DBN) and the like, tertiary amines such as triethylamine,N,N-diisopropylethylamine and the like, and the like. The amount of thebase used is usually 1 mol or more per 1 mol of the compound (20).

[Compound (18)→Compound (23)]

Examples of a chlorinating agent used in the reaction include oxalyldichloride, thionyl chloride and the like. The amount of thechlorinating agent used is usually 1 to 10 mol per 1 mol of the compound(18).

The reaction is performed under a solventless condition or in a solvent.Examples of the solvent include ethers such as 1,4-dioxane, diethylether, methyl tert-butyl ether and the like, halogenated hydrocarbonssuch as dichloromethane, chloroform, carbon tetrachloride,1,2-dichloroethane, chlorobenzene and the like, hydrocarbons such astoluene, benzene, xylene and the like, nitriles such as acetonitrile andthe like, and a mixture thereof.

[Compound (23)→Compound (24)]

The reaction is usually performed in a solvent. Examples of the solventinclude ethers such as 1,4-dioxane, diethyl ether, tetrahydrofuran,methyl tert-butyl ether and the like, halogenated hydrocarbons such asdichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane,chlorobenzene and the like, hydrocarbons such as toluene, benzene,xylene and the like, nitriles such as acetonitrile and the like, aproticpolar solvents such as N,N-dimethylformamide, N-methylpyrrolidone,1,3-dimethyl-2-imidazolidinone, dimethyl sulfoxide and the like, and amixture thereof.

The amount of the compound (21) used in the reaction is usually 1 molper 1 mol of the compound (23).

The reaction is performed in the presence of a base, as necessary.Example of the base include nitrogen-containing heterocyclic compoundssuch as pyridine, picoline, 2,6-lutidine1,8-diazabicyclo[5.4.0]7-undecene (DBU), 1,5-diazabicyclo[4.3.0]5-nonene(DBN) and the like, tertiary amines such as triethylamine,N,N-diisopropylethylamine and the like, and the like. The amount of thebase used is usually 1 mol or more per 1 mol of the compound (23).

[Compound (24)→Compound (22)]

Examples of H-L⁴ include hydrogen chloride and hydrogen bromide.

The reaction is usually performed in a solvent. Examples of the solventinclude ethers such as 1,4-dioxane, diethyl ether, methyl tert-butylether and the like, halogenated hydrocarbons such as dichloromethane,chloroform, carbon tetrachloride, 1,2-dichloroethane, chlorobenzene andthe like, hydrocarbons such as toluene, benzene, xylene and the like,and a mixture thereof.

[Compound (22)→Compound (25)]

The reaction is performed in the presence of a base. Examples of thebase used in the reaction include metal carbonates such as sodiumcarbonate, potassium carbonate, sodium hydrogen carbonate, potassiumhydrogen carbonate, calcium carbonate, cesium carbonate and the like.The amount of the base used is usually 1 mol or more per 1 mol of thecompound (22).

The reaction is usually performed in a solvent. Examples of the solventinclude ethers such as 1,4-dioxane, diethyl ether, tetrahydrofuran,methyl tert-butyl ether and the like, halogenated hydrocarbons such asdichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane,chlorobenzene and the like, hydrocarbons such as toluene, benzene,xylene and the like, nitriles such as acetonitrile and the like, aproticpolar solvents such as N,N-dimethylformamide, N-methylpyrrolidone,1,3-dimethyl-2-imidazolidinone, dimethyl sulfoxide and the like, and amixture thereof.

[Compound (25)→Compound (26)]

Examples of a halogenating agent used in the reaction include oxalyldichloride, thionyl chloride, phosphorus oxychloride, phosphoruspentachloride, thionyl bromide, phosphorus oxybromide, phosphoruspentabromide and the like. The amount of the halogenating agent used isusually 1 to 10 mol per 1 mol of the compound (25).

The reaction is performed under a solventless condition or in a solvent.Examples of the solvent include ethers such as 1,4-dioxane, diethylether, methyl tert-butyl ether and the like, halogenated hydrocarbonssuch as dichloromethane, chloroform, carbon tetrachloride,1,2-dichloroethane, chlorobenzene and the like, hydrocarbons such astoluene, benzene, xylene and the like, nitriles such as acetonitrile andthe like, and a mixture thereof.

[Compound (25)→Compound (27)]

Examples of Cl—SO₂R^(d) include methanesulfonyl chloride,benzenesulfonyl chloride, p-toluenesulfonyl chloride and the like. Theamount of Cl—SO₂R^(d) used is usually 1 mol per 1 mol of the compound(25).

The reaction is usually performed in a solvent. Examples of the solventinclude ethers such as 1,4-dioxane, diethyl ether, tetrahydrofuran,methyl tert-butyl ether and the like, halogenated hydrocarbons such asdichloromethane, dibromomethane, chloroform, bromoform, carbontetrachloride, 1,2-dichloroethane, chlorobenzene and the like,hydrocarbons such as toluene, benzene, xylene and the like, nitrilessuch as acetonitrile and the like, aprotic polar solvents such asN,N-dimethylformamide, N-methylpyrrolidone,1,3-dimethyl-2-imidazolidinone, dimethyl sulfoxide and the like, and amixture thereof.

The reaction is performed in the presence of a base, as necessary.Example of the base include nitrogen-containing heterocyclic compoundssuch as pyridine, picoline, 2,6-lutidine1,8-diazabicyclo[5.4.0]7-undecene (DBU), 1,5-diazabicyclo[4.3.0]5-nonene(DBN) and the like, tertiary amines such as triethylamine,N,N-diisopropylethylamine and the like, and the like. The amount of thebase used is usually 1 mol or more per 1 mol of the compound (25).

[Compound (27)→Compound (26)]

Examples of H—X² include hydrogen chloride and hydrogen bromide.

The reaction is usually performed in a solvent. Examples of the solventinclude ethers such as 1,4-dioxane, diethyl ether, methyl tert-butylether and the like, halogenated hydrocarbons such as dichloromethane,dibromomethane, chloroform, bromoform, carbon tetrachloride,1,2-dichloroethane, chlorobenzene and the like, hydrocarbons such astoluene, benzene, xylene and the like, carboxylic acids such as aceticacid and the like, and a mixture thereof.

[Compound (26)→Compound (17-i)]

Examples of an oxidizing agent used in the reaction include persulfatessuch as sodium persulfate, potassium persulfate, ammonium persulfate andthe like, quinone compounds such as2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ),tetrachloro-1,4-benzoquinone (p-chloranil), tetrabromo-1,4-benzoquinone(p-bromanil), tetrachloro-1,2-benzoquinone (o-chloranil),tetrabromo-1,2-benzoquinone (o-bromanil) and the like, halogens such aschlorine, bromine and the like, air, and the like.

In the case of using a persulfate as the oxidizing agent, the amount ofthe oxidizing agent is usually 1 to 2 mol per 1 mol of the compound(26), and the reaction is usually performed in a solvent and examplesthereof include nitriles such as acetonitrile and the like; water; and amixture thereof.

In the case of using a quinone compound as the oxidizing agent, theamount of the oxidizing agent is usually 1 to 2 mol per 1 mol of thecompound (26). The reaction is usually performed in a solvent andexamples of thereof include ethers such as 1,4-dioxane, diethyl ether,tetrahydrofuran, methyl tert-butyl ether and the like; halogenatedhydrocarbons such as dichloromethane, chloroform, bromoform, carbontetrachloride, 1,2-dichloroethane, chlorobenzene and the like;hydrocarbons such as hexane, heptane, toluene, benzene, xylene and thelike; nitriles such as acetonitrile and the like; amides such asN,N-dimethylformamide and the like; nitrogen-containing heterocycliccompounds such as N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone,and the like; aprotic polar solvents, for example, sulfoxide solventssuch as dimethyl sulfoxide and the like; carboxylic acids such as aceticacid and the like; ketones such as acetone, isobutyl methyl ketone andthe like; esters such as ethyl acetate and the like; alcohols such as2-propanol, tert-butyl alcohol and the like, and water. Two or more ofthe above-mentioned solvents may be used as a mixture, and the reactionmay be performed in a single-phase system or a two-phase system.

In the case of using a halogen atom as the oxidizing agent, the reactionis performed in the presence of a solvent and a base as necessary. Theamount of the oxidizing agent is usually 1 mol to an excess amount per 1mol of the compound (26). Examples of the solvent usually used in thereaction include halogenated hydrocarbons such as dichloromethane,dibromomethane, chloroform, bromoform, carbon tetrachloride,1,2-dichloroethane, chlorobenzene and the like, hydrocarbons such astoluene, benzene, xylene and the like, and a mixture thereof. Examplesof the base include metal carbonates such as sodium carbonate, potassiumcarbonate, sodium hydrogen carbonate, potassium hydrogen carbonate,calcium carbonate, cesium carbonate and the like. The amount of the baseused is usually 1 mol or more per 1 mol of the compound (26).

In the case of using air as the oxidizing agent, the reaction isperformed in the presence of a solvent and a catalyst as necessary.Examples of the solvent usually used in the reaction include halogenatedhydrocarbons such as dichloromethane, dibromomethane, chloroform, carbontetrachloride, 1,2-dichloroethane, chlorobenzene and the like,hydrocarbons such as toluene, benzene, xylene and the like, and amixture thereof. Examples of the catalyst include metal halides such asiron(III) chloride, iron(III) bromide and the like. The amount of thecatalyst used is usually 0.001 to 1 mol per 1 mol of the compound (26).

The compound (1), the compound (2) and their intermediate compoundsdescribed above can be isolated and purified by a conventional methodsuch as liquid separation, filtration, recrystallization, columnchromatography, high performance column chromatography (HPLC), mediumpressure preparative HPLC, desalting resin column chromatography,re-precipitation, distillation or the like.

Then, each substituent represented by R¹, R², R³, R⁴, R⁵, R⁶ and R⁷ inthe compound (1), the compound (2) and the compound (3) will beexplained.

Examples of the “halogen atom” include a fluorine atom, a chlorine atom,a bromine atom and an iodine atom.

Examples of the “C1-C6 alkyl group optionally substituted with at leastone halogen atom” include a methyl group, a trifluoromethyl group, atrichloromethyl group, a chloromethyl group, a dichloromethyl group, afluoromethyl group, a difluoromethyl group, an ethyl group, apentafluoroethyl group, a 2,2,2-trifluoroethyl group, a2,2,2-trichloroethyl group, a propyl group, an isopropyl group, aheptafluoroisopropyl group, a butyl group, an isobutyl group, asec-butyl group, a tert-butyl group, a pentyl group and a hexyl group.

Examples of the “C3-C6 alkoxyalkyl group optionally substituted with atleast one halogen atom” include a 2-methoxyethyl group, a 2-ethoxyethylgroup and a 2-isopropyloxyethyl group.

Examples of the “C2-C6 alkenyl group optionally substituted with atleast one halogen atom” include a 2-propenyl group, a3-chloro-2-propenyl group, a 2-chloro-2-propenyl group, a3,3-dichloro-2-propenyl group, a 2-butenyl group, a 3-butenyl group, a2-methyl-2-propenyl group, a 3-methyl-2-butenyl group, a 2-pentenylgroup and a 2-hexenyl group.

Examples of the “C3-C6 alkynyl group optionally substituted with atleast one halogen atom” include a 2-propynyl group, a3-chloro-2-propynyl group, a 3-bromo-2-propynyl group, a 2-butynyl groupand a 3-butynyl group.

Examples of the “C1-C6 alkoxy group optionally substituted with at leastone halogen atom” include a methoxy group, an ethoxy group, a2,2,2-trifluoroethoxy group, a propoxy group, an isopropyloxy group, abutoxy group, an isobutyloxy group, a sec-butoxy group and a tert-butoxygroup.

Examples of the “C1-C6 alkylthio group optionally substituted with atleast one halogen atom” include a methylthio group, atrifluoromethylthio group, an ethylthio group, a propylthio group, anisopropylthio group, a butylthio group, an isobutylthio group, asec-butylthio group, a tert-butylthio group, a pentylthio group and ahexylthio group.

Example of the “C1-C6 alkylsulfinyl group optionally substituted with atleast one halogen atom” include a methylsulfinyl group, atrifluoromethylsulfinyl group, an ethylsulfinyl group, a propylsulfinylgroup, an isopropylsulfinyl group, a butylsulfinyl group, anisobutylsulfinyl group, a sec-butylsulfinyl group, a tert-butylsulfinylgroup, a pentylsulfinyl group and a hexylsulfinyl group.

Examples of the “C1-C6 alkylsulfonyl group optionally substituted withat least one halogen atom” include a methylsulfonyl group, atrifluoromethylsulfonyl group, an ethylsulfonyl group, a propylsulfonylgroup, an isopropylsulfonyl group, a butylsulfonyl group, anisobutylsulfonyl group, a sec-butylsulfonyl group, a tert-butylsulfonylgroup, a pentylsulfonyl group and a hexylsulfonyl group.

Examples of the compound (1) include the following aspects:

a compound represented by the formula (1) wherein R² is a C1-C6 alkylgroup optionally substituted with at least one halogen atom;

a compound represented by the formula (1) wherein R² is a hydrogen atom;

a compound represented by the formula (1) wherein R¹ is a methyl groupor an ethyl group and R² is a hydrogen atom, a methyl group or an ethylgroup;

a compound represented by the formula (1) wherein R¹ and R² are methylgroups;

a compound represented by the formula (1) wherein R¹ is a methyl groupand R² is a hydrogen atom;

a compound represented by the formula (1) wherein R¹ is an ethyl groupand R² is a hydrogen atom;

a compound represented by the formula (1) wherein R³ is a C1-C6 alkylgroup optionally substituted with at least one halogen atom;

a compound represented by the formula (1) wherein R³ is a methyl groupor an ethyl group;

a compound represented by the formula (1) wherein R⁴ is a halogen atomor a methyl group;

a compound represented by the formula (1) wherein R⁵ is a halogen atomor a cyano group;

a compound represented by the formula (1) wherein R⁴ is a halogen atomor a methyl group and R⁵ is a halogen atom or a cyano group;

a compound represented by the formula (1) wherein R¹ is a methyl groupor an ethyl group, R² is a hydrogen atom, a methyl group or an ethylgroup, R³ is a methyl group or an ethyl group, R⁴ is a halogen atom or amethyl group, and R⁵ is a halogen atom or a cyano group;

a compound represented by the formula (1) wherein R¹, R² and R³ aremethyl groups, R⁴ is a chlorine atom, a bromine atom or a methyl group,and R⁵ is a chlorine atom, a bromine atom or a cyano group;

a compound represented by the formula (1) wherein R¹ is a methyl group,R² is a hydrogen atom, R³ is a methyl group, R⁴ is a chlorine atom, abromine atom or a methyl group, and R⁵ is a chlorine atom, a bromineatom or a cyano group; and

a compound represented by the formula (1) wherein R¹ is an ethyl group,R² is a hydrogen atom, R³ is a methyl group, R⁴ is a chlorine atom, abromine atom or a methyl group, and R⁵ is a chlorine atom, a bromineatom or a cyano group.

Examples of the compound (2) include the following aspects:

a compound represented by the formula (2) wherein R⁶ is a halogen atomor a C1-C6alkyl group optionally substituted with at least one halogenatom;

a compound represented by the formula (2) wherein R⁶ is a halogen atomor a trifluoromethyl group;

a compound represented by the formula (2) wherein R⁷ is a halogen atom;

a compound represented by the formula (2) wherein R⁶ is a halogen atomor a trifluoromethyl group and R⁷ is a halogen atom; and

a compound represented by the formula (2) wherein R⁶ is a chlorine atom,a bromine atom or a trifluoromethyl group and R⁷ is a chlorine atom.

Examples of the compound (3) include the following aspects:

a compound represented by the formula (3) wherein R² is a C1-C6 alkylgroup optionally substituted with at least one halogen atom;

a compound represented by the formula (3) wherein R² is a hydrogen atom;

a compound represented by the formula (3) wherein R¹ is a methyl groupor an ethyl group and R² is a hydrogen atom, a methyl group or an ethylgroup;

a compound represented by the formula (3) wherein R¹ and R² are methylgroups;

a compound represented by the formula (3) wherein R¹ is a methyl groupand R² is a hydrogen atom;

a compound represented by the formula (3) wherein R¹ is an ethyl groupand R² is a hydrogen atom;

a compound represented by the formula (3) wherein R³ is a C1-C6 alkylgroup optionally substituted with at least one halogen atom;

a compound represented by the formula (3) wherein R³ is a methyl groupor an ethyl group;

a compound represented by the formula (3) wherein R⁴ is a halogen atomor a methyl group;

a compound represented by the formula (3) wherein R⁵ is a halogen atomor a cyano group;

a compound represented by the formula (3) wherein R⁴ is a halogen atomor a methyl group and R⁵ is a halogen atom or a cyano group;

a compound represented by the formula (3) wherein R⁶ is a halogen atomor a C1-C6 alkyl group optionally substituted with at least one halogenatom;

a compound represented by the formula (3) wherein R⁶ is a halogen atomor a trifluoromethyl group;

a compound represented by the formula (3) wherein R⁷ is a halogen atom;

a compound represented by the formula (3) wherein R⁶ is a halogen atomor a trifluoromethyl group and R⁷ is a halogen atom;

a compound represented by the formula (3) wherein R¹ is a methyl groupor an ethyl group, R² is a hydrogen atom, a methyl group or an ethylgroup, R³ is a methyl group or an ethyl group, R⁴ is a halogen atom or amethyl group, R⁵ is a halogen atom or a cyano group, R⁶ is a halogenatom or a trifluoromethyl group, and R⁷ is a halogen atom;

a compound represented by the formula (3) wherein R¹, R² and R³ aremethyl groups, R⁴ is a chlorine atom, a bromine atom or a methyl group,R⁵ is a chlorine atom, a bromine atom or a cyano group, R⁶ is a chlorineatom, a bromine atom or a trifluoromethyl group, and R⁷ is a chlorineatom;

a compound represented by the formula (3) wherein R¹ is a methyl group,R² is a hydrogen atom, R³ is a methyl group, R⁴ is a chlorine atom, abromine atom or a methyl group, R⁵ is a chlorine atom, a bromine atom ora cyano group, R⁶ is a chlorine atom, a bromine atom or atrifluoromethyl group, and R⁷ is a chlorine atom; and

a compound represented by the formula (3) wherein R¹ is an ethyl group,R² is a hydrogen atom, R³ is a methyl group, R⁴ is a chlorine atom, abromine atom or a methyl group, R⁵ is a chlorine atom, a bromine atom ora cyano group, R⁶ is a chlorine atom, a bromine atom or atrifluoromethyl group, and R⁷ is a chlorine atom.

Examples of the compound (17) include the following aspects:

a compound represented by the formula (17) wherein R⁶ is a halogen atomor a C1-C6 alkyl group optionally substituted with at least one halogenatom;

a compound represented by the formula (17) wherein R⁶ is a halogen atomor a trifluoromethyl group;

a compound represented by the formula (17) wherein R⁷ is a halogen atom;

a compound represented by the formula (17) wherein R⁶ is a halogen atomor a trifluoromethyl group, and R⁷ is a halogen atom; and

a compound represented by the formula (17) wherein R⁶ is a chlorineatom, a bromine atom or a trifluoromethyl group, and R⁷ is a chlorineatom.

The compound (3) produced by the process of the present invention has anexcellent controlling activity on harmful arthropods. Examples ofharmful arthropods that can be controlled by the compound (3) includearthropods as mentioned below.

Hemiptera:

Planthoppers (Delphacidae) such as small brown planthopper (Laodelphaxstriatellus), brown rice planthopper (Nilaparvata lugens), andwhite-backed rice planthopper (Sogatella furcifera); leafhoppers(Deltocephalidae) such as green rice leafhopper (Nephotettixcincticeps), green rice leafhopper (Nephotettix virescens), and teagreen leafhopper (Empoasca onukii); aphids (Aphididae) such as cottonaphid (Aphis gossypii), green peach aphid (Myzus persicae), cabbageaphid (Brevicoryne brassicae), spiraea aphid (Aphis spiraecola), potatoaphid (Macrosiphum euphorbiae), foxglove aphid (Aulacorthum solani), oatbird-cherry aphid (Rhopalosiphum padi), tropical citrus aphid (Toxopteracitricidus), and mealy plum aphid (Hyalopterus pruni); stink bugs(Pentatomidae) such as green stink bug (Nezara antennata), bean bug(Riptortus clavetus), rice bug (Leptocorisa chinensis), white spottedspined bug (Eysarcoris parvus), and stink bug (Halyomorpha mista);whiteflies (Aleyrodidae) such as greenhouse whitefly (Trialeurodesvaporariorum), sweetpotato whitefly (Bemisia tabaci), silver leafwhitefly (Bemisia argentifolii), citrus whitefly (Dialeurodes citri),and citrus spiny white fly (Aleurocanthus spiniferus); scales (Coccidae)such as California red scale (Aonidiella aurantii), San Jose scale(Comstockaspis perniciosa), citrus north scale (Unaspis citri), red waxscale (Ceroplastes rubens), cottonycushion scale (Icerya purchasi),Japanese mealybug (Planococcus kraunhiae), Cosmstock mealybug(Pseudococcus longispinis), and white peach scale (Pseudaulacaspispentagona); lace bugs (Tingidae); psyllids (Psyllidae); etc.

Lepidoptera:

Pyralid moths (Pyralidae) such as rice stem borer (Chilo suppressalis),yellow rice borer (Tryporyza incertulas), rice leafroller(Cnaphalocrocis medinalis), cotton leafroller (Notarcha derogata),Indian meal moth (Plodia interpunctella), oriental corn borer (Ostriniafurnacalis), cabbage webworm (Hellula undalis), and bluegrass webworm(Pediasia teterrellus); owlet moths (Noctuidae) such as common cutworm(Spodoptera litura), beet armyworm (Spodoptera exigua), armyworm(Pseudaletia separata), cabbage armyworm (Mamestra brassicae), blackcutworm (Agrotis ipsilon), beet semi-looper (Plusia nigrisigna),Thoricoplusia spp., Heliothis spp., and Helicoverpa spp.; whites andsulfer butterflies (Pieridae) such as common white (Pieris rapae);tortricid moths (Tortricidae) such as Adoxophyes spp., oriental fruitmoth (Grapholita molesta), soybean pod borer (Leguminivoraglycinivorella), azuki bean podworm (Matsumuraeses azukivora), summerfruit tortrix (Adoxophyes orana fasciata), smaller tea tortrix(Adoxophyes sp.), oriental tea tortrix (Homona magnanima), apple tortrix(Archips fuscocupreanus), and codling moth (Cydia pomonella); leafblotchminers (Gracillariidae) such as tea leafroller (Caloptilia theivora),and apple leafminer (Phyllonorycter ringoneella); Carposinidae such aspeach fruit moth (Carposina niponensis); lyonetiid moths (Lyonetiidae)such as Lyonetia spp.; tussock moths (Lymantriidae) such as Lymantriaspp., and Euproctis spp.; yponomeutid moths (Yponomeutidae) such asdiamondback (Plutella xylostella); gelechiid moths (Gelechiidae) such aspink bollworm (Pectinophora gossypiella), and potato tubeworm(Phthorimaea operculella); tiger moths and allies (Arctiidae) such asfall webworm (Hyphantria cunea); tineid moths (Tineidae) such ascasemaking clothes moth (Tinea translucens), and webbing clothes moth(Tineola bisselliella); etc.

Thysanoptera:

Thrips (Thripidae) such as yellow citrus thrips (Frankliniellaoccidentalis), Thrips parmi, yellow tea thrips (Scirtothrips dorsalis),onion thrip (Thrips tabaci), flower thrips (Frankliniella intonsa), etc.

Diptera:

Housefly (Musca domestica), common mosquito (Culex popiens pallens),horsefly (Tabanus trigonus), onion maggot (Hylemya antiqua), seedcornmaggot (Hylemya platura), Anopheles sinensis, rice leafminer (Agromyzaoryzae), rice leafminer (Hydrellia griseola), rice stem maggot (Chloropsoryzae), melon fly (Dacus cucurbitae), Ceratitis capitata, legumeleafminer (Liriomyza trifolii), tomato leafminer (Liriomyza sativae),garden pea leafminer (Chromatomyia horticola), etc.

Coleoptera:

Twenty-eight-spotted ladybird (Epilachna vigintioctopunctata), cucurbitleaf beetle (Aulacophora femoralis), striped flea beetle (Phyllotretastriolata), rice leaf beetle (Oulema oryzae), rice curculio(Echinocnemus squameus), rice water weevil (Lissorhoptrus oryzophilus),Anthonomus grandis, azuki bean weevil (Callosobruchus chinensis),Sphenophorus venatus, Japanese beetle (Popillia japonica), cupreouschafer (Anomala cuprea), corn root worms (Diabrotica spp.), Coloradobeetle (Leptinotarsa decemlineata), click beetles (Agriotes spp.),cigarette beetle (Lasioderma serricorne), varied carper beetle(Anthrenus verbasci), red flour beetle (Tribolium castaneum), powderpost beetle (Lyctus brunneus), white-spotted longicorn beetle(Anoplophora malasiaca), pine shoot beetle (Tomicus piniperda), etc.

Orthoptera:

Asiatic locust (Locusta migratoria), African mole cricket (Gryllotalpaafricana), rice grasshopper (Oxya yezoensis), rice grasshopper (Oxyajaponica), etc.

Hymenoptera:

Cabbage sawfly (Athalia rosae), leaf-cutting ant (Acromyrmex spp.), fireant (Solenopsis spp.), etc.

Blattodea:

German cockroach (Blattella germanica), smokybrown cockroach(Periplaneta fuliginosa), American cockroach (Periplaneta americana),Periplaneta brunnea, oriental cockroach (Blatta orientalis), etc.

Acarina:

Spider mites (Tetranychidae) such as two-spotted spider mite(Tetranychus urticae), Kanzawa spider mite (Tetranychus kanzawai),citrus red mite (Panonychus citri), European red mite (Panonychus ulmi),and Oligonychus spp.; eriophyid mites (Eriophyidae) such as pink citrusrust mite (Aculops pelekassi), pink citrus rust mite (Phyllocoptrutacitri), tomato rust mite (Aculops lycopersici), purple tea mite(Calacarus carinatus), pink tea rust mite (Acaphylla theavagran), andEriophyes chibaensis; tarosonemid mites (Tarsonemidae) such as broadmite (Polyphagotarsonemus latus); false spider mites (Tenuipalpidae)such as Brevipalpus phoenicis; Tuckerellidae; ticks (Ixodidae) such asHaemaphysalis longicornis, Haemaphysalis flava, Dermacentor taiwanicus,Ixodes ovatus, Ixodes persulcatus, Boophilus microplus, andRhipicephalus sanguineus; acarid mites (Acaridae) such as mold mite(Tyrophagus putrescentiae), and Tyrophagus similis; house dust mites(Pyroglyphidae) such as Dermatophagoides farinae, and Dermatophagoidesptrenyssnus; cheyletide mites (Cheyletidae) such as Cheyletus eruditus,Cheyletus malaccensis, and Cheyletus moorei; parasitoid mites(Dermanyssidae); etc.

When the compound (3) is used for controlling harmful arthropods,although the compound (3) may be used as it is, a pesticidal compositioncomprising the compound (3) as an active ingredient is usually used. Thepesticidal composition is obtained by mixing the compound (3) with aninert carrier such as a solid carrier, a liquid carrier or a gaseouscarrier and further with, if necessary, a surfactant and otherpharmaceutical additives to be formulated into a preparation such as anemulsion, an oil preparation, a powder, a granule, a wettable powder, aflowable preparation, a microcapsule, an aerosol, a fumigant, a poisonbait, a resin preparation or the like. The pesticidal composition thusobtained usually contains 0.01 to 95% by weight of the compound (3).

Examples of the solid carrier used for formulation includefinely-divided powder or granules of clay (e.g., kaolin clay,diatomaceous earth, bentonite, Fubasami clay, acid clay, etc.),synthetic hydrated silicon oxide, talc, ceramics, other inorganicminerals (e.g., sericite, quartz, sulfur, activated carbon, calciumcarbonate, hydrated silica, etc.), chemical fertilizers (e.g., ammoniumsulfate, ammonium phosphate, ammonium nitrate, ammonium chloride, urea,etc.) and the like.

Examples of the liquid carrier used for formulation include water,alcohols (methanol, ethanol, isopropyl alcohol, butanol, hexanol, benzylalcohol, ethylene glycol, propylene glycol, phenoxyethanol etc.),ketones (acetone, methyl ethyl ketone, cyclohexanone etc.), aromatichydrocarbons (toluene, xylene, ethylbenzene, dodecylbenzene,phenylxylylethane, methylnaphthalene etc.), aliphatic hydrocarbons(hexane, cyclohexane, kerosene, gas oil etc.), esters (ethyl acetate,butyl acetate, isopropyl myristate, ethyl oleate, diisopropyl adipate,diisobutyl adipate, propylene glycol monomethyl ether acetate etc.),nitriles (acetonitrile, isobutyronitrile etc.), ethers (diisopropylether, 1,4-dioxane, ethylene glycol dimethyl ether, diethylene glycoldimethyl ether, diethylene glycol monomethyl ether, propylene glycolmonomethyl ether, dipropylene glycol monomethyl ether,3-methoxy-3-methyl-1-butanol etc.), acid amides (N,N-dimethylformamide,N,N-dimethylacetamide etc.), halogenated hydrocarbons (dichloromethane,trichloroethane, carbon tetrachloride etc.), sulfoxides (dimethylsulfoxide etc.), propylene carbonate and vegetable oils (soybean oil,cottonseed oil etc.).

Examples of the gaseous carrier used for formulation includefluorocarbon, butane gas, LPG (liquefied petroleum gas), dimethyl etherand carbon dioxide gas.

Examples of the surfactant include nonionic surfactants such aspolyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether,polyethylene glycol fatty acid ester and the like, and anionicsurfactants such as alkyl sulfonate salt, alkylbenzene sulfonate salt,alkyl sulfate salt and the like.

Examples of other pharmaceutical additives include a binder, adispersant, a coloring agent and a stabilizer, and specific examplesthereof include casein, gelatin, saccharides (starch, gum arabic,cellulose derivatives, alginic acid etc.), lignin derivatives,bentonite, synthetic water-soluble polymers (polyvinyl alcohol,polyvinylpyrrolidone, polyacrylic acid etc.), PAP (isopropyl acidphosphate), BHT (2,6-di-tert-butyl-4-methylphenol), and BHA (a mixtureof 2-tert-butyl-4-methoxyphenol and 3-tert-butyl-4-methoxyphenol).

For controlling harmful arthropods, the compound (3) can be used as itis or as a pesticidal composition containing the compound (3) asdescribed above. Usually, a pesticidal composition containing thecompound (3) as described above is used for controlling harmfularthropods. A method for controlling harmful arthropods comprisesapplying the compound (3) or a pesticidal composition containing thecompound (3) to harmful arthropods or a place where harmful arthropodsinhabit by the same method as that of applying a known pesticide.

Examples of the place where harmful arthropods inhabit include paddyfields, cultivated lands, orchards, non-crop lands, houses and the like.

Examples of the application method include spraying treatment, soiltreatment, seed treatment, water culture medium treatment and the like.

The spraying treatment is a treatment method which comprises treatingthe plant surfaces or harmful arthropods themselves with an activeingredient and thereby can produce a controlling effect on harmfularthropods. Specific examples of the spraying treatment include sprayingtreatment to foliage, spraying treatment to tree trunks and the like.

The soil treatment is a treatment method which comprises treating soilor an irrigation liquid with an active ingredient for the purpose ofallowing the active ingredient to permeate and transfer into theinterior of the plant body of a crop to be protected from damage such asingestion by harmful arthropods through the root part or the like of theplant, and thereby can protect the crop from damage by harmfularthropods. Specific examples of the soil treatment include plantinghole treatment (spraying into planting holes, soil mixing after plantinghole treatment), plant foot treatment (plant foot spraying, soil mixingafter plant foot treatment, irrigation at plant foot, plant foottreatment at a later seeding raising stage), planting furrow treatment(planting furrow spraying, soil mixing after planting furrow treatment),planting row treatment (planting row spraying, soil mixing afterplanting row treatment, planting row spraying at a growing stage),planting row treatment at the time of sowing (planting row spraying atthe time of sowing, soil mixing after planting row treatment at the timeof sowing), broadcast treatment (overall soil surface spraying, soilmixing after broadcast treatment), other soil spraying treatment(spraying of a granular formulation on leaves at a growing stage,spraying under a canopy or around a tree stem, spraying on the soilsurface, mixing with surface soil, spraying into seed holes, spraying onthe ground surfaces of furrows, spraying between plants), otherirrigation treatment (soil irrigation, irrigation at a seedling raisingstage, drug solution injection treatment, irrigation of a plant partjust above the ground, drug solution drip irrigation, chemigation),seedling raising box treatment (spraying into a seedling raising box,irrigation of a seedling raising box), seedling raising tray treatment(spraying on a seedling raising tray, irrigation of a seedling raisingtray), seedbed treatment (spraying on a seedbed, irrigation of aseedbed, spraying on a lowland rice nursery, immersion of seedlings),seedbed soil incorporation treatment (mixing with seedbed soil, mixingwith seedbed soil before sowing), and other treatment (mixing withculture soil, plowing under, mixing with surface soil, mixing with soilat the place where raindrops fall from a canopy, treatment at a plantingposition, spraying of a granule formulation on flower clusters, mixingwith a paste fertilizer).

The seed treatment is a treating method which comprises applying anactive ingredient directly to or around a seed, a seed tuber or a bulbof a crop to be protected from damage such as ingestion by harmfularthropods and thereby can produce a controlling effect on harmfularthropods. Specific examples of the seed treatment include sprayingtreatment, spray coating treatment, immersion treatment, impregnationtreatment, coating treatment, film coating treatment, and pellet coatingtreatment.

The water culture medium treatment is a treating method which comprisestreating a water culture medium or the like with an active ingredientfor the purpose of allowing the active ingredient to permeate andtransfer into the interior of the plant body of a crop to be protectedfrom damage such as ingestion by harmful arthropods through the rootpart or the like of the plant, and thereby can protect the crop fromdamage by harmful arthropods. Specific examples of the water culturemedium treatment include mixing with a water culture medium,incorporation into a water culture medium, and the like.

When a pesticidal composition comprising the compound (3) is used forcontrolling harmful arthropods in the field of agriculture, theapplication amount thereof is usually 1 to 10,000 g of the compound (3)per 10,000 m². When a pesticidal composition comprising the compound (3)is in the form of a preparation such as an emulsion, a wettable powderor a flowable preparation, the composition is usually applied after itis diluted with water so that the active ingredient concentrationbecomes 0.01 to 10,000 ppm. When a pesticidal composition comprising thecompound (3) is in the form of a preparation such as a granule or apowder, the composition is usually applied as it is.

Such a pesticidal composition comprising the compound (3) or awater-dilution thereof may be directly sprayed to harmful arthropods orplants such as crops to be protected from harmful arthropods.Alternatively, soil of a cultivated land may be treated with thecomposition comprising the compound (3) or a water-dilution thereof inorder to control harmful arthropods which inhabit the soil.

A pesticidal composition comprising the compound (3) may be in the formof a resin preparation which is processed into a sheet or a string. Sucha resin preparation can be applied by winding a crop with a sheet or astring of the resin preparation, putting a string of the resinpreparation around a crop so that the crop is surrounded by the string,or laying a sheet of the resin preparation on the soil surface near theroot of a crop.

When a pesticidal composition comprising the compound (3) is used forcontrolling harmful arthropods living in a house (e.g. fly, mosquito,cockroach), the application amount thereof is usually 0.01 to 1,000 mgof the compound (3) per 1 m² in the case of plain surface treatment, andis usually 0.01 to 500 mg of the compound (3) per 1 m³ in the case ofspace treatment. When a pesticidal composition comprising the compound(3) is in the form of a preparation such as an emulsion, a wettablepowder or a flowable preparation, the composition is usually appliedafter it is diluted with water so that the active ingredientconcentration becomes 0.1 to 1,000 ppm. When a pesticidal compositioncomprising the compound (3) is in the form of a preparation such as anoil preparation, an aerosol preparation, a fumigant or a poison bait,the composition is usually applied as it is.

The compound (3) can be used as an insecticide for crop lands such ascultivated lands, paddy fields, lawns and orchards, or non-crop lands.The compound produced by the process of the present invention cancontrol pests in crop lands and the like where plants including cropsand the like listed below are cultivated without causing drug damage tothe crops, in some cases.

Agricultural crops: corn, rice, wheat, barley, rye, oat, sorghum,cotton, soybean, peanut, sarrazin, sugar beet, rapeseed, sunflower,sugar cane, tobacco etc.;

Vegetables: Solanaceae vegetables (eggplant, tomato, green pepper, hotpepper, potato etc.), Cucurbitaceae vegetables (cucumber, pumpkin,zucchini, watermelon, melon etc.), Cruciferae vegetables (Japaneseradish, turnip, horseradish, kohlrabi, Chinese cabbage, cabbage, brownmustard, broccoli, cauliflower etc.), Compositae vegetables (burdock,garland chrysanthemum, artichoke, lettuce etc.), Liliaceae vegetables(Welsh onion, onion, garlic, asparagus etc.), Umbelliferae vegetables(carrot, parsley, celery, parsnip etc.), Chenopodiaceae vegetables(spinach, Swiss chard etc.), Labiatae vegetables (Japanese basil, mint,basil etc.), strawberry, sweat potato, yam, aroid etc.;

Flowers and ornamental plants;

Foliage plant;

Fruit trees: pomaceous fruits (apple, common pear, Japanese pear,Chinese quince, quince etc.), stone fleshy fruits (peach, plum,nectarine, Japanese plum, cherry, apricot, prune etc.), citrus plants(Satsuma mandarin, orange, lemon, lime, grapefruit etc.), nuts(chestnut, walnut, hazel nut, almond, pistachio, cashew nut, macadamianut etc.), berry fruits (blueberry, cranberry, blackberry, raspberryetc.), vine, persimmon, olive, loquat, banana, coffee, date, coconutetc.;

Trees other than fruit trees: tea, mulberry, flowering trees and shrubs,street trees (ash tree, birch, dogwood, eucalyptus, ginkgo, lilac, mapletree, oak, poplar, cercis, Chinese sweet gum, plane tree, zelkova,Japanese arborvitae, fir tree, Japanese hemlock, needle juniper, pine,spruce, yew) etc.

Hereinafter, the present invention will be explained in more detail byreference to Examples, but the present invention is not limited toExamples.

EXAMPLES Example 1

A mixture of 0.33 g of the compound (1-1):

0.24 g of the compound (2-1):

0.25 g of o-chloranil and 2 ml of 1,4-dioxane was stirred and heatedunder reflux under a nitrogen atmosphere for 7 hours. The reactionmixture was allowed to cool to room temperature. After an aqueoussolution of sodium hydrogen carbonate was added, the reaction mixturewas extracted with ethyl acetate. The organic layer was washed withwater, dried over anhydrous magnesium sulfate, and concentrated underreduced pressure. The resulting residue was subjected to silica gelcolumn chromatography to obtain 0.35 g of the compound (3-1).

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.71 (1.4H, s), 2.83 (1.6H, s), 2.94(1.5H, s), 3.06 (1.5H, s), 3.35-3.70 (3.0H, m), 7.41 (0.5H, s), 7.45(0.6H, s), 7.47 (0.6H, s), 7.60-7.64 (1.3H, m), 8.07 (0.5H, d, J=2 Hz),8.13 (0.5H, s), 8.18 (1.0H, d, J=8 Hz), 8.50 (1.0H, m), 10.52 (0.5H, s),10.67 (0.5H, s).

Example 2

A mixture of 0.42 g of the compound (1-1), 0.31 g of the compound (2-1),0.32 g of p-chloranil, 0.004 g of p-toluenesulfonic acid monohydrate and3 ml of 1,4-dioxane was stirred and heated under reflux under a nitrogenatmosphere for 4 hours. The reaction mixture was allowed to cool to roomtemperature. After an aqueous solution of sodium hydrogen carbonate wasadded, the reaction mixture was extracted with ethyl acetate. Theorganic layer was washed with water, dried over anhydrous magnesiumsulfate, and concentrated under reduced pressure. The resulting residuewas subjected to silica gel column chromatography to obtain 0.37 g ofthe compound (3-1).

Example 3

A mixture of 0.26 g of the compound (1-1), 0.19 g of the compound (2-1),0.19 g of o-chloranil, 0.017 g of titanium (IV) isopropoxide and 2 ml of1,4-dioxane was stirred and heated under reflux under a nitrogenatmosphere for 7 hours. The reaction mixture was allowed to cool to roomtemperature. After an aqueous solution of sodium hydrogen carbonate wasadded, the reaction mixture was extracted with ethyl acetate. Theorganic layer was washed with water, dried over anhydrous magnesiumsulfate, and concentrated under reduced pressure. The resulting residuewas subjected to silica gel column chromatography to obtain 0.20 g ofthe compound (3-1).

Example 4

A mixture of 0.65 g of the compound (1-2):

0.47 g of the compound (2-1), 0.48 g of p-chloranil, a catalytic amountof p-toluenesulfonic acid monohydrate and 4 ml of 1,4-dioxane wasstirred and heated under reflux under a nitrogen atmosphere for 11hours. Thereto was added additional 0.20 g of p-chloranil, and themixture was stirred and heated under reflux for 6 hours. The reactionmixture was allowed to cool to room temperature. After water was added,the reaction mixture was extracted with ethyl acetate. The organic layerwas washed with sequentially a 2N sodium hydroxide aqueous solution,water and a saturated sodium chloride aqueous solution, dried overanhydrous magnesium sulfate, and then concentrated under reducedpressure. The resulting residue was subjected to silica gel columnchromatography to obtain 0.55 g of the compound (3-2).

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 0.86 (1.0H, t, J=7 Hz), 0.99 (2.0H, t,J=7 Hz), 3.10 (1.7H, brs), 3.50 (2.4H, s), 3.64 (0.6H, s), 3.85 (0.3H,brs), 7.36-7.44 (2.0H, m), 7.59-7.65 (1.0H, m), 8.07-8.21 (2.0H, m),8.49-8.51 (1.0H, m), 9.04 (0.7H, brs), 9.71 (0.3H, brs), 10.30 (0.7H,brs), 10.66 (0.3H, brs).

Example 5

A mixture of 0.096 g of the compound (1-4):

0.072 g of the compound (2-1), 0.075 g of o-chloranil, a catalyticamount of p-toluenesulfonic acid monohydrate, a catalytic amount ofcopper iodide and 1 ml of 1,4-dioxane was stirred and heated underreflux under a nitrogen atmosphere for 3.5 hours. The reaction mixturewas allowed to cool to room temperature. After a 1N aqueous solution ofsodium hydroxide was added, the reaction mixture was extracted withethyl acetate. The organic layer was washed with water, dried overanhydrous magnesium sulfate, and concentrated under reduced pressure.The resulting residue was subjected to silica gel column chromatographyto obtain 0.078 g of the compound (3-4).

¹H-NMR (100° C., DMSO-d₆, TMS) δ (ppm): 2.96 (3H, s), 3.04 (3H, brs),7.30 (1H, s), 7.38 (1H, s), 7.58 (1H, dd, J=8 Hz, 5 Hz), 7.96 (1H, s),8.11 (1H, d, J=8 Hz), 8.47 (1H, d, J=5 Hz), 8.68 (1H, brs), 10.08 (1H,brs).

Example 6

A mixture of 0.20 g of the compound (1-1), 0.12 g of the compound (2-3):

0.15 g of p-chloranil, 0.002 g of p-toluenesulfonic acid monohydrate and1 ml of 1,4-dioxane was stirred and heated under reflux under a nitrogenatmosphere for 1 hours. The reaction mixture was allowed to cool to roomtemperature. After a sodium hydrogen carbonate aqueous solution wasadded, the reaction mixture was extracted with ethyl acetate. Theorganic layer was washed with water, dried over anhydrous magnesiumsulfate, and then concentrated under reduced pressure. The resultingresidue was subjected to silica gel column chromatography to obtain 0.21g of the compound (3-16).

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.71 (1.4H, s), 2.83 (1.6H, s), 2.94(1.3H, brs), 3.06-3.08 (1.7H, m), 3.44-3.68 (3.0H, m), 7.36-7.47 (2.0H,m), 7.60-7.64 (1.0H, m), 8.08-8.20 (2.0H, m), 8.50-8.51 (1.0H, m), 10.56(0.4H, brs), 10.71 (0.6H, brs).

Specific examples of the compound (3) which can be produced by theprocess of the present invention are listed below.

TABLE 1 Com- pound No. R¹ R² R³ R⁴ R⁵ R⁶ R⁷ 3-1 CH₃ CH₃ CH₃ Br Br Br Cl3-2 CH₃CH₂ H CH₃ Br Br Br Cl 3-3 CH₃ H CH₃ CH₃ Cl Br Cl 3-4 CH₃ H CH₃ BrBr Br Cl 3-5 (CH₃)₂CH H CH₃ Br Br Br Cl 3-6 CH₃ H CH₃ CH₃ Cl CF₃ Cl 3-7CH₃ CH₃ CH₃ CH₃ Cl Br Cl 3-8 CH₃ H CH₃ CH₃ CN Br Cl 3-9 CH₃ CH₃ CH₃ CH₃CN Br Cl 3-10 CH₃ H CH₃ Cl Cl Br Cl 3-11 CH₃ H CH₃CH₂ Cl Cl Br Cl 3-12CH₃ CH₃ CH₃ Cl Cl Br Cl 3-13 CH₃ CH₃ CH₃ Br Cl Br Cl 3-14 CH₃ CH₃ CH₃CH₃ Cl Cl Cl 3-15 CH₃ CH₃ CH₃ Cl Cl Cl Cl 3-16 CH₃ CH₃ CH₃ Br Br Cl Cl3-17 CH₃CH₂ H CH₃ Cl Cl Br Cl 3-18 CH₃ CH₃ CH₃ Br Br CF₃ Cl 3-19CH₃(CH₂)₂ H CH₃ Br Br Br Cl 3-20 CH₃ CH₃CH₂ CH₃ Br Br Br Cl 3-21 CH₃CH₂CH₃ CH₃ Br Br Br Cl 3-22 CH₃CH₂ CH₃CH₂ CH₃ Br Br Br Cl 3-23 CH₃CH₂ H CH₃CH₃ Cl Br Cl 3-24 CH₃CH₂ H CH₃ CH₃ CN Br Cl 3-25 CH₃CH₂ H CH₃ Br Br ClCl 3-26 CH₃CH₂ H CH₃ Cl Cl Cl Cl 3-27 CH₃CH₂ H CH₃ CH₃ Cl Cl Cl 3-28CH₃CH₂ H CH₃ CH₃ CN Cl Cl 3-29 CH₃CH₂ H CH₃ Br Br CF₃ Cl 3-30 CH₃CH₂ HCH₃ Cl Cl CF₃ Cl 3-31 CH₃CH₂ H CH₃ CH₃ Cl CF₃ Cl 3-32 CH₃CH₂ H CH₃ CH₃CN CF₃ Cl 3-33 CH₃ H CH₃ Br Br CF₃ Cl 3-34 CH₃ H CH₃ Br Br Cl Cl 3-35CH₃ H CH₃ Cl Cl Cl Cl 3-36 CH₃ H CH₃ CH₃ Cl Cl Cl 3-37 CH₃ H CH₃ CH₃ CNCl Cl 3-38 CH₃ H CH₃ Cl Cl CF₃ Cl 3-39 CH₃ H CH₃ CH₃ CN CF₃ Cl 3-40 CH₃CH₃ CH₃ CH₃ CN Cl Cl 3-41 CH₃ CH₃ CH₃ Cl Cl CF₃ Cl 3-42 CH₃ CH₃ CH₃ CH₃Cl CF₃ Cl 3-43 CH₃ CH₃ CH₃ CH₃ CN CF₃ Cl

Physical properties of some compounds (3) are shown.

Compound (3-1)

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.71 (1.4H, s), 2.83 (1.6H, s), 2.94(1.5H, s), 3.06 (1.5H, s), 3.35-3.70 (3.0H, m), 7.41 (0.5H, s), 7.45(0.6H, s), 7.47 (0.6H, s), 7.60-7.64 (1.3H, m), 8.07 (0.5H, d, J=2 Hz),8.13 (0.5H, s), 8.18 (1.0H, d, J=8 Hz), 8.50 (1.0H, m), 10.52 (0.5H, s),10.67 (0.5H, s).

Compound (3-2)

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 0.86 (1.0H, t, J=7 Hz), 0.99 (2.0H, t,J=7 Hz), 3.10 (1.7H, brs), 3.50 (2.4H, s), 3.64 (0.6H, s), 3.85 (0.3H,brs), 7.36-7.44 (2.0H, m), 7.59-7.65 (1.0H, m), 8.07-8.21 (2.0H, m),8.49-8.51 (1.0H, m), 9.04 (0.7H, brs), 9.71 (0.3H, brs), 10.30 (0.7H,brs), 10.66 (0.3H, brs).

Compound (3-3)

¹H-NMR (CDCl₃, TMS) δ (ppm): 2.04 (3H, s), 3.22 (3H, s), 3.57 (2.6H, s),3.80 (0.4H, s), 7.01 (1H, s), 7.04 (1H, s), 7.28 (1H, s), 7.40 (1H, dd,J=8 Hz, 5 Hz), 7.61 (1H, brs), 7.87 (1H, dd, J=8 Hz, 2 Hz), 8.46 (1H,dd, J=5 Hz, 2 Hz), 9.80 (1H, brs).

Compound (3-4)

¹H-NMR (100° C., DMSO-d₆, TMS) δ (ppm): 2.96 (3H, s), 3.04 (3H, brs),7.30 (1H, s), 7.38 (1H, s), 7.58 (1H, dd, J=8 Hz, 5 Hz), 7.96 (1H, s),8.11 (1H, d, J=8 Hz), 8.47 (1H, d, J=5 Hz), 8.68 (1H, brs), 10.08 (1H,brs).

Compound (3-5)

¹H-NMR (CDCl₃, TMS) δ (ppm): 0.87-0.95 (3.8H, m), 1.13-1.26 (4.4H, m),3.55 (2.5H, s), 3.81 (0.5H, s), 4.55-4.67 (1.0H, m), 7.37-7.42 (3.0H,m), 7.49 (1.0H, d, J=2 Hz), 7.57 (1.1H, d, J=2 Hz), 7.86 (1.0H, dd, J=8Hz, 2 Hz), 8.45 (1.0H, dd, J=5 Hz, 2 Hz), 9.68 (0.3H, brs), 9.93 (0.7H,brs).

Compound (3-6)

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.11 (3H, s), 3.06 (3H, s), 3.33 (3H, s),7.07 (1H, s), 7.45 (1H, s), 7.68 (1H, s), 7.69 (1H, dd, J=8 Hz, 4 Hz),8.24 (1H, d, J=8 Hz), 8.55 (1H, d, J=4 Hz), 9.11 (0.6H, brs), 10.20 (1H,brs), 10.54 (0.4H, brs).

Compound (3-7)

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.10-2.24 (3H, m), 2.61-2.87 (3H, m),2.90-3.18 (3H, m), 3.45-3.74 (3H, m), 7.12-7.30 (1H, m), 7.33-7.44 (1H,m), 7.44-7.58 (1H, m), 7.58-7.66 (1H, m), 8.20 (1H, d, J=8 Hz),8.47-8.54 (1H, m), 10.10-10.50 (1H, m).

Compound (3-8)

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.21 (3H, s), 3.08 (3H, s), 3.45-3.70(3H, m), 7.30-7.43 (1H, m), 7.44-7.61 (1H, m), 7.63 (1H, dd, J=8 Hz, 5Hz), 7.82-7.94 (1H, m), 8.21 (1H, d, J=8 Hz, 1 Hz), 8.51 (1H, dd, J=5Hz, 1 Hz), 9.21 (1H, brs), 10.24 (1H, brs).

Compound (3-9)

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.14-2.29 (3H, m), 2.64-2.87 (3H, m),2.87-3.15 (3H, m), 3.42-3.73 (3H, m), 7.30-7.45 (1H, m), 7.54-7.81 (2H,m), 7.83-8.01 (1H, m), 8.15-8.24 (1H, m), 8.50 (1H, brs), 10.20-10.68(1H, m).

Compound (3-10)

¹H-NMR (CDCl₃, TMS) δ (ppm): 3.12-3.18 (3H, brm), 3.60-3.84 (3H, brm),7.21-7.22 (2H, m), 7.34 (1H, brs), 7.41 (1H, dd, J=8 Hz, 5 Hz), 7.51(1H, brs), 7.88 (1H, dd, J=8 Hz, 1 Hz), 8.48 (1H, dd, J=5 Hz, 1 Hz),9.85 (1H, brs).

Compound (3-11)

¹H-NMR (CDCl₃, TMS) δ (ppm): 1.11-1.39 (3H, m), 3.12-3.18 (3H, brm),4.06-4.25 (2H, brm), 7.08-7.22 (2H, m), 7.34 (1H, brs), 7.41 (1H, dd,J=8 Hz, 5 Hz), 7.43 (1H, brs), 7.88 (1H, dd, J=8 Hz, 1 Hz), 8.49 (1H,dd, J=5 Hz, 1 Hz), 9.87 (1H, brs).

Compound (3-12)

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.73 (1.4H, s), 2.83 (1.6H, s), 2.95(1.6H, s), 3.07 (1.4H, s), 3.49-3.68 (3.0H, m), 7.32-7.44 (2.0H, m),7.62 (1.0H, dd, J=8 Hz, 5 Hz), 7.85 (0.5H, d, J=2 Hz), 7.92 (0.5H, s),8.19 (1.0H, dd, J=8 Hz, 1 Hz), 8.49-8.52 (1.0H, m), 10.53 (0.5H, s),10.71 (0.5H, s).

Compound (3-13)

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.72 (1.4H, s), 2.83 (1.6H, s), 2.94(1.6H, s), 3.07 (1.4H, s), 3.49-3.68 (3.0H, m), 7.34-7.45 (2.0H, m),7.60-7.64 (1.0H, m), 7.98 (0.4H, d, J=2 Hz), 8.04 (0.5H, s), 8.19 (1.0H,d, J=8 Hz), 8.49-8.52 (1.0H, m), 10.54 (0.5H, s), 10.70 (0.5H, s).

Compound (3-14)

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.13 (1.4H, s), 2.18 (1.6H, s), 2.73(1.4H, s), 2.82 (1.6H, s), 2.93-2.96 (1.2H, m), 3.07-3.07 (1.8H, m),3.43-3.69 (3.0H, m), 7.18-7.32 (2.0H, m), 7.46-7.53 (1.0H, m), 7.60-7.64(1.0H, m), 8.19 (1.0H, d, J=8 Hz), 8.49-8.51 (1.0H, m), 10.20 (0.4H,brs), 10.45 (0.6H, brs).

Compound (3-15)

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.73 (1.3H, s), 2.84 (1.7H, s), 2.95(1.3H, brs), 3.07-3.08 (1.7H, m), 3.46-3.68 (3.0H, m), 7.32-7.39 (2.0H,m), 7.62 (1.0H, dd, J=8 Hz, 5 Hz), 7.85-7.92 (1.0H, m), 8.19 (1.0H, d,J=8 Hz), 8.49-8.51 (1.0H, m), 10.54 (0.4H, brs), 10.74 (0.6H, brs).

Compound (3-16)

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.71 (1.4H, s), 2.83 (1.6H, s), 2.94(1.3H, brs), 3.06-3.08 (1.7H, m), 3.44-3.68 (3.0H, m), 7.36-7.47 (2.0H,m), 7.60-7.64 (1.0H, m), 8.08-8.20 (2.0H, m), 8.50-8.51 (1.0H, m), 10.56(0.4H, brs), 10.71 (0.6H, brs).

Compound (3-17)

¹H-NMR (CDCl₃, TMS) δ (ppm): 1.03-1.07 (3.0H, m), 3.31-3.82 (5.0H, m),7.23 (2.0H, s), 7.31 (1.0H, s), 7.39 (1.0H, dd, J=8 Hz, 5 Hz), 7.54(1.0H, s), 7.87 (1.0H, dd, J=8 Hz, 1 Hz), 8.46 (1.0H, dd, J=5 Hz, 1 Hz),9.65 (0.2H, brs), 9.86 (0.8H, brs).

Compound (3-18)

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.71 (1.4H, s), 2.84 (1.6H, s), 2.95(1.3H, brs), 3.07 (1.7H, s), 3.45-3.70 (3.0H, brm), 7.48 (1.0H, brs),7.66-7.71 (1.0H, m), 7.77-7.80 (1.0H, m), 8.12 (1.0H, d, J=21 Hz), 8.24(1.0H, dd, J=8 Hz, 1 Hz), 8.53-8.55 (1.0H, m), 10.72 (0.4H, brs), 10.85(0.6H, brs).

Compound (3-19)

¹H-NMR (CDCl₃, TMS) δ (ppm): 0.88-0.95 (3H, m), 1.48 (2H, tq, J=8 Hz, 8Hz), 3.22-3.83 (5H, brm), 7.37-7.44 (3H, m), 7.56 (1H, d, J=2 Hz), 7.61(1H, s), 7.86 (1H, dd, J=8 Hz, 2 Hz), 8.46 (1H, dd, J=5 Hz, 2 Hz), 9.77(0.3H, s), 9.98 (0.7H, s).

Compound (3-20)

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 0.79-1.00 (3.0H, m), 2.88 (2.2H, d, J=12Hz), 3.01-3.08 (1.0H, m), 3.12 (0.8H, s), 3.15-3.22 (1.0H, m), 3.45-3.69(3.0H, m), 7.41-7.47 (2.0H, m), 7.60-7.64 (1.0H, m), 8.10-8.20 (2.0H,m), 8.49-8.52 (1.0H, m), 10.50 (0.3H, brs), 10.70 (0.7H, brs).

Compound (3-21)

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 0.86-0.91 (2.0H, m), 1.11-1.14 (1.0H, m),2.75 (1.0H, s), 2.85-3.23 (4.0H, brm), 3.64-3.73 (3.0H, m), 7.41-7.46(2.0H, m), 7.60-7.63 (1.0H, m), 8.07-8.19 (2.0H, m), 8.48-8.50 (1.0H,m), 10.48 (0.3H, brs), 10.67 (0.7H, brs).

Compound (3-22)

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 0.86-1.15 (6.0H, brm), 3.08-3.29 (3.0H,brm), 3.37-3.74 (4.0H, brm), 7.43-7.47 (2.0H, m), 7.61-7.65 (1.0H, m),8.10-8.20 (2.0H, m), 8.49-8.51 (1.0H, m), 10.47 (0.3H, brs), 10.65-10.76(0.7H, brm).

Compound (3-23)

¹H-NMR (CDCl₃, TMS) δ (ppm): 1.06 (3H, t, J=7 Hz), 2.04 (3H, s),3.56-3.78 (5H, m), 7.02 (1H, s), 7.06 (1H, s), 7.20-7.26 (1H, m), 7.38(1H, dd, J=8 Hz, 5 Hz), 7.62 (1H, s), 7.86 (1H, dd, J=8 Hz, 2 Hz), 8.44(1H, dd, J=5 Hz, 2 Hz), 9.82 (1H, brs).

Compound (3-25)

¹H-NMR (CDCl₃, TMS) δ (ppm): 1.04 (3H, t, J=7 Hz), 3.45-3.90 (5H, m),7.23 (1H, s), 7.40 (1H, dd, J=8 Hz, 5 Hz), 7.45 (1H, d, J=2 Hz), 7.54(1H, s), 7.60 (1H, d, J=2 Hz), 7.87 (1H, dd, J=8 Hz, 2 Hz), 8.46 (1H,dd, J=5 Hz, 2 Hz), 9.67 (1H, brs).

Compound (3-26)

¹H-NMR (CDCl₃, TMS) δ (ppm): 1.05 (3H, t, J=7 Hz), 3.43-3.69 (5H, m),7.19-7.22 (3H, m), 7.40 (1H, dd, J=8 Hz, 5 Hz), 7.53 (1H, s), 7.87 (1H,d, J=8 Hz), 8.46 (1H, d, J=5 Hz), 9.82 (1H, brs).

Compound (3-27)

¹H-NMR (CDCl₃, TMS) δ (ppm): 1.06 (3H, t, J=7 Hz), 2.04 (3H, s),3.45-3.95 (5H, m), 7.02 (1H, s), 7.06 (1H, s), 7.17 (1H, s), 7.38 (1H,dd, J=8 Hz, 5 Hz), 7.63 (1H, s), 7.86 (1H, dd, J=8 Hz, 2 Hz), 8.44 (1H,dd, J=5 Hz, 2 Hz), 9.83 (1H, brs).

Compound (3-29)

¹H-NMR (CDCl₃, TMS) δ (ppm): 1.04 (3H, t, J=7 Hz), 3.41-3.83 (5H, m),7.42-7.45 (2H, m), 7.55-7.58 (2H, m), 7.70 (1H, s), 7.89 (1H, dd, J=8Hz, 2 Hz), 8.48 (1H, dd, J=5 Hz, 2 Hz), 10.20 (1H, brs).

Compound (3-30)

¹H-NMR (CDCl₃, TMS) δ (ppm): 1.05 (3H, t, J=7 Hz), 3.45-3.95 (5H, m),7.35 (1H, s), 7.39 (1H, dd, J=8 Hz, 5 Hz), 7.43 (1H, d, J=2 Hz),7.55-7.59 (2H, m), 7.86 (1H, dd, J=8 Hz, 2 Hz), 8.46 (1H, dd, J=5 Hz, 2Hz), 9.86 (1H, brs).

Compound (3-31)

¹H-NMR (CDCl₃, TMS) δ (ppm): 1.05 (3H, t, J=7 Hz), 1.99 (3H, s),3.45-3.95 (5H, m), 6.97 (1H, s), 7.04 (1H, s), 7.42 (1H, dd, J=8 Hz, 5Hz), 7.65 (1H, s), 7.67 (1H, s), 7.88 (1H, d, J=8 Hz), 8.46 (1H, d, J=5Hz), 10.27 (1H, brs).

Compound (3-33)

¹H-NMR (CDCl₃, TMS) δ (ppm): 3.18 (3H, s), 3.60-3.85 (3H, m), 7.42-7.46(2H, m), 7.55-7.58 (2H, m), 7.72 (1H, s), 7.90 (1H, dd, J=8 Hz, 2 Hz),8.49 (1H, dd, J=5 Hz, 2 Hz), 10.14 (1H, brs).

Then, examples of production of the compound (1) and the compound (2)will be described as Reference Production Examples.

Reference Production Example 1

(1) To a mixture of 1.85 g of methyl carbazate and 60 ml oftetrahydrofuran was added 6.0 g of6,8-dibromo-2H-3,1-benzoxazine-2,4-1H-dione

(a compound described in Journal of Organic Chemistry (1947), 12,743-51) under ice-cooling, and the mixture was stirred for 3 hours underice-cooling. The reaction mixture was warmed to room temperature, and0.46 g of methyl carbazate was further added thereto. The mixture wasstirred at room temperature for 15 hours, and then concentrated underreduced pressure. To the resulting residue was added water, and theremaining solid was filtered. The solid was washed sequentially withwater and ethyl acetate to obtain 4.96 g ofN-(2-amino-3,5-dibromobenzoyl)-N′-methoxycarbonylhydrazine.

N-(2-amino-3,5-dibromobenzoyl)-N′-methoxycarbonylhydrazine

¹H-NMR (DMSO-d₆) δ: 3.63 (3H, s), 6.55 (2H, s), 7.71 (1H, s), 7.79 (1H,s), 9.25 (1H, s), 10.32 (1H, s).

(2) To a mixture of 3.67 g ofN-(2-amino-3,5-dibromobenzoyl)-N′-methoxycarbonylhydrazine, 3.04 g ofpotassium carbonate and 50 ml of N-methylpyrrolidone was added dropwisea mixture of 3.12 g of methyl iodide and 2 ml of1-methyl-2-pyrrolidinone under ice-cooling. The mixture was stirred for4 hours under ice-cooling, and then stirred at room temperature for 3hours. After water was added, the reaction mixture was extracted withethyl acetate. The organic layer was washed with water, dried overanhydrous magnesium sulfate, and concentrated under reduced pressure.The resulting residue was subjected to silica gel column chromatographyto obtain 2.83 g of the compound (1-1).

Compound (1-1)

¹H-NMR (CDCl₃, TMS) δ (ppm): 3.11-3.18 (6H, m), 3.76 (3H, brs), 4.86(1.4H, brs), 5.23 (0.6H, brs), 7.17-7.25 (1H, m), 7.57 (1H, d, J=2 Hz).

Reference Production Example 2

(1) To a mixture of 0.61 g of ethylhydrazine oxalate, 1.0 g of6,8-dibromo-2H-3,1-benzoxazine-2,4-1H-dione and 10 ml of tetrahydrofuranwas added 1.12 g of potassium carbonate under ice-cooling, and themixture was stirred at room temperature for 1.5 hours. After water wasadded, the reaction mixture was extracted with ethyl acetate. Theorganic layer was washed sequentially with water and a saturatedsolution of sodium chloride, dried over anhydrous magnesium sulfate, andconcentrated under reduced pressure. The resulting residue was subjectedto silica gel column chromatography to obtain 0.44 g ofN-(2-amino-3,5-dibromobenzoyl)-N-ethylhydrazine and 0.13 g ofN-(2-amino-3,5-dibromobenzoyl)-N′-ethylhydrazine.

N-(2-amino-2-3,5-dibromobenzoyl)-N-ethylhydrazine

¹H-NMR (CDCl₃, TMS) δ (ppm): 1.25 (3H, t, J=7 Hz), 3.52 (2H, q, J=7 Hz),4.38 (2H, brs), 4.81 (2H, brs), 7.21 (1H, d, J=2 Hz), 7.59 (1H, d, J=2Hz).

N-(2-amino-2,3,5-dibromobenzoyl)-N′-ethylhydrazine

¹H-NMR (CDCl₃, TMS) δ (ppm): 1.15 (3H, t, J=7 Hz), 2.95 (2H, q, J=7 Hz),4.78 (1H, brs), 6.02 (2H, brs), 7.38 (1H, d, J=2 Hz), 7.52 (1H, brs),7.64 (1H, d, J=2 Hz).

(2) To a mixture of 0.42 g ofN-(2-amino-3,5-dibromobenzoyl)-N-ethylhydrazine and 3 ml of pyridine wasadded 0.15 g of methyl chloroformate under ice-cooling, and the mixturewas stirred for 1 hour under ice-cooling. After water was added, thereaction mixture was concentrated under reduced pressure. Water wasadded to the resulting residue, followed by extraction with ethylacetate. The organic layer was washed sequentially with water and asaturated solution of sodium chloride, dried over anhydrous magnesiumsulfate, and concentrated under reduced pressure. The resulting residuewas subjected to silica gel column chromatography to obtain 0.42 g ofthe compound (1-2).

Compound (1-2)

¹H-NMR (CDCl₃, TMS) δ (ppm): 1.21 (3H, t, J=7 Hz), 3.62 (2H, q, J=7 Hz),3.78 (3H, s), 4.95 (2H, brs), 6.96 (1H, brs), 7.26 (1H, d, J=2 Hz), 7.59(1H, d, J=2 Hz).

Reference Production Example 3

(1) To a mixture of 10.0 g of6,8-dibromo-2H-3,1-benzoxazine-2,4-1H-dione and 90 ml of tetrahydrofuranwas added 1.58 g of methylhydrazine under ice-cooling, and the mixturewas stirred at room temperature for 4 hours. After water was added, thereaction mixture was extracted with ethyl acetate. The organic layer waswashed with a saturated solution of sodium chloride, dried overanhydrous magnesium sulfate, and concentrated under reduced pressure.The resulting residue was subjected to silica gel column chromatographyto obtain 4.64 g of N-(2-amino-3,5-dibromobenzoyl)-N-methylhydrazine and0.75 g of N-(2-amino-3,5-dibromobenzoyl)-N′-methylhydrazine.

N-(2-amino-3,5-dibromobenzoyl)-N-methylhydrazine

¹H-NMR (CDCl₃, TMS) δ (ppm): 3.25 (3H, s), 4.55 (2H, brs), 4.89 (2H,brs), 7.23 (1H, s), 7.59 (1H, s).

N-(2-amino-3,5-dibromobenzoyl)-N′-methylhydrazine

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.51 (3H, s), 5.11 (1H, brs), 6.54 (2H,s), 7.63 (1H, d, J=2 Hz), 7.73 (1H, d, J=2 Hz), 10.06 (1H, brs).

(2) To a mixture of 3.40 g ofN-(2-amino-3,5-dibromobenzoyl)-N-methylhydrazine and 30 ml oftetrahydrofuran were added 2.2 g of triethylamine and 2.0 g of methylchloroformate under ice-cooling, and the mixture was stirred at roomtemperature. After water was added, the reaction mixture was extractedwith ethyl acetate. The organic layer was washed with a saturatedsolution of sodium chloride, dried over anhydrous magnesium sulfate, andconcentrated under reduced pressure. The resulting residue was subjectedto silica gel column chromatography to obtain 1.10 g of the compound(1-4).

Compound (1-4)

¹H-NMR (CDCl₃, TMS) δ (ppm): 3.28 (3H, s), 3.76 (3H, s), 4.96 (2H, brs),7.00 (1H, brs), 7.27 (1H, d, J=2 Hz), 7.59 (1H, d, J=2 Hz).

Reference Production Example 4

(1) A mixture of 10.7 g of 3-bromo-1H-pyrazole, 11.8 g of2,3-dichloropyridine, 57.3 g of cesium carbonate and 80 ml ofN,N-dimethylformamide was stirred at 100° C. for 8 hours. The reactionmixture was allowed to cool to room temperature. After water was added,and the reaction mixture was extracted with methyl tert-butyl ether twotimes. The organic layers were combined, washed with sequentially withwater and a saturated solution of sodium chloride, dried over magnesiumsulfate, and concentrated under reduced pressure. The resulting residuewas subjected to silica gel column chromatography to obtain 12.9 g of2-(3-bromo-1H-pyrazol-1-yl)-3-chloropyridine.

2-(3-Bromo-1H-pyrazol-1-yl)-3-chloropyridine

¹H-NMR (CDCl₃, TMS) δ (ppm): 6.51 (1H, d, J=2 Hz), 7.31 (1H, dd, J=8 Hz,4 Hz), 7.91 (1H, dd, J=8 Hz, 1 Hz), 8.04 (1H, d, J=2 Hz), 8.45 (1H, dd,J=4 Hz, 1 Hz).

(2) To a mixture of 5.0 g of2-(3-bromo-1H-pyrazol-1-yl)-3-chloropyridine and 30 ml oftetrahydrofuran was added dropwise 11.7 ml of a 2.0M solution of lithiumdiisopropylamide in heptane/tetrahydrofuran/ethylbenzene. To thereaction mixture was added dropwise a mixture of 3 g of ethyl formateand 10 ml of tetrahydrofuran at −78° C., and the mixture was stirred atroom temperature for 2 hours. After water was added, the reactionmixture was extracted with ethyl acetate. The organic layer was washedwith water, dried over anhydrous magnesium sulfate, and concentratedunder reduced pressure. The resulting residue was subjected to silicagel column chromatography to obtain 3.0 g of the compound (2-1).

Compound (2-1)

¹H-NMR (CDCl₃, TMS) δ (ppm): 7.11 (1H, s), 7.47 (1H, dd, J=8 Hz, 5 Hz),7.96 (1H, dd, J=8 Hz, 1 Hz), 8.52 (1H, dd, J=5 Hz, 1 Hz), 9.79 (1H, s).

Reference Production Example 5

(1) According to the process of Reference Production Example 4(1) exceptthat 3-trifluoromethyl-1H-pyrazole was used in place of3-bromo-1H-pyrazole,3-chloro-2-(3-trifluoromethyl-1H-pyrazol-1-yl)pyridine was obtained.

3-Chloro-2-(3-trifluoromethyl-1H-pyrazol-1-yl)pyridine

¹H-NMR (CDCl₃, TMS) δ (ppm): 6.75 (1H, d, J=2 Hz), 7.37 (1H, dd, J=8 Hz,4 Hz), 7.95 (1H, dd, J=8 Hz, 1 Hz), 8.14 (1H, d, J=1 Hz), 8.49 (1H, dd,J=4 Hz, 1 Hz).

(2) According to the process of Reference Production Example 4(2) exceptthat 3-chloro-2-(3-trifluoromethyl-1H-pyrazol-1-yl)pyridine is used inplace of 2-(3-bromo-1H-pyrazol-1-yl)-3-chloropyridine, the compound(2-2) was obtained.

¹H-NMR (CDCl₃, TMS) δ (ppm): 7.36 (1H, s), 7.51 (1H, dd, J=8 Hz, 5 Hz),7.99 (1H, dd, J=8 Hz, 2 Hz), 8.54 (1H, dd, J=5 Hz, 2 Hz), 9.86 (1H, s).

Reference Production Example 6

(1) According to the process of Reference Production Example 4(1) exceptthat 3-chloro-1H-pyrazole was used in place of 3-bromo-1H-pyrazole,2-(3-chloro-1H-pyrazol-1-yl)-3-chloropyridine was obtained.

2-(3-Chloro-1H-pyrazol-1-yl)-3-chloropyridine

¹H-NMR (CDCl₃, TMS) δ (ppm): 6.43 (1H, d, J=3 Hz), 7.30 (1H, dd, J=8 Hz,5 Hz), 7.91 (1H, dd, J=8 Hz, 2 Hz), 8.09 (1H, d, J=2 Hz), 8.44 (1H, dd,J=5 Hz, 1 Hz).

(2) According to the process of Reference Production Example 4(2) exceptthat 2-(3-chloro-1H-pyrazol-1-yl)-3-chloropyridine is used in place of2-(3-bromo-1H-pyrazol-1-yl)-3-chloropyridine, the compound (2-3) wasobtained.

Compound (2-3)

¹H-NMR (CDCl₃, TMS) δ (ppm): 7.02 (1H, s), 7.47 (1H, dd, J=8 Hz, 5 Hz),7.97 (1H, dd, J=8 Hz, 2 Hz), 8.51 (1H, dd, J=5 Hz, 2 Hz), 9.79 (1H, s).

Reference Production Example 7

(1) To a mixture of 10 g of methyl carbazate and 60 ml of toluene wasadded dropwise a mixture of 5.86 g of acetaldehyde and 20 ml of tolueneat 50° C., and the mixture was stirred for 1 hour. The reaction mixturewas cooled with ice, and a solid precipitated was filtered. The solidwas dried to obtain 12.1 g of N′-ethylidenehydrazinecarboxylic acidmethyl ester.

N′-ethylidenehydrazinecarboxylic acid methyl ester

¹H-NMR (CDCl₃, TMS) δ (ppm): 1.99 (3H, d, J=5 Hz), 3.82 (3H, s), 7.24(1H, q, J=5 Hz), 8.31 (1H, brs).

(2) To a mixture of 5.0 g of N′-ethylidenehydrazinecarboxylic acidmethyl ester and 50 ml of tetrahydrofuran were added sequentially 1.95 gof sodium borohydride and 4.2 ml of methanol at 50° C., and the mixturewas stirred for 3 hours at 50° C. To the reaction mixture was added 50ml of methanol at 50° C., and then the mixture was stirred and heatedunder reflux for 3 hours. The reaction mixture was concentrated underreduced pressure, and 20 ml of chloroform was added to the residue. Themixture was stirred at 50° C. for 10 minutes and then filtered withcelite. The resulting filtrate was concentrated under reduced pressureand the residue was subjected to silica gel column chromatography toobtain 3.70 g of N′-ethylhydrazinecarboxylic acid methyl ester.

N′-ethylhydrazinecarboxylic acid methyl ester

¹H-NMR (DMSO-D₆, TMS) δ (ppm): 0.93 (3H, t, J=7 Hz), 2.66-2.73 (2H, m),3.54 (3H, s), 4.38-4.43 (1H, m), 8.45 (1H, s).

(3) To a mixture of 0.50 g of N′-ethylhydrazinecarboxylic acid methylester and 4 ml of tetrahydrofuran was added 1.36 g of6,8-dibromo-2H-3,1-benzoxadine-2,4-1H-dione at room temperature. Themixture was stirred and heated under reflux for 4 hours, and then cooledto room temperature. After water was added, the reaction mixture wasextracted with ethyl acetate. The organic layer was washed with asaturated sodium chloride aqueous solution, dried over anhydrousmagnesium sulfate, and then concentrated under reduced pressure. Theresulting residue was subjected to silica gel column chromatography toobtain 0.89 g of the compound (1-2).

Reference Production Example 8

(1) A mixture of 1.16 g of 4-methoxycrotonic acid (a compound describedin Journal of Organic Chemistry, 1981, 46, 940-948) and 10 ml of diethylether was cooled with ice, and thereinto hydrogen chloride gas wasintroduced. After the mixture was saturated with hydrogen chloride gas,it was allowed to stand at room temperature overnight. A sample obtainedfrom the reaction mixture was subjected to NMR analysis to confirm theproduction of 3-chloro-4-methoxybutyric acid. All amount of the reactionmixture obtained was used as it is for the following step.

3-Chloro-4-methoxybutyric acid

¹H-NMR (CDCl₃, TMS) δ (ppm): 2.76 (1H, dd, J=17.9 Hz), 3.00 (1H, dd,J=17 Hz, 5 Hz), 3.42 (3H, s), 3.56 (1H, dd, J=10 Hz, 7 Hz), 3.65 (1H,dd, J=10 Hz, 5 Hz), 4.36-4.42 (1H, m).

(2) To the reaction mixture obtained in the above step (1), 2.54 g ofoxalyl dichloride was added dropwise under ice-cooling. To the reactionmixture was added a drop of N,N-dimethylformamide, and the mixture wasstirred at room temperature for 2 hours. The reaction mixture wasconcentrated under reduced pressure to obtain 1.45 g of3-chloro-4-methoxybutyryl chloride.

3-Chloro-4-methoxybutyryl chloride

¹H-NMR (CDCl₃, TMS) δ (ppm): 3.26 (1H, dd, J=18 Hz, 9 Hz), 3.41 (3H, s),3.49-3.54 (2H, m), 3.66 (1H, dd, J=10 Hz, 5 Hz), 4.35-4.41 (1H, m).

(3) To a mixture of 1.29 g of 3-chloro-2-hydrazinopyridine, 1.07 g ofpyridine and 10 ml of N,N-dimethylformamide was added dropwise a mixtureof 1.45 g of 3-chloro-4-methoxybutyryl chloride and 5 ml of tolueneunder ice-cooling. The mixture was stirred at room temperature for 2hours. After water was added, the reaction mixture was extracted withethyl acetate. The organic layer was washed with water and a saturatedsodium chloride aqueous solution, dried over anhydrous sodium sulfate,and then concentrated under reduced pressure to obtain 1.86 g of thecompound (22-1).

¹H-NMR (CDCl₃, TMS) δ (ppm): 2.73 (1H, dd, J=15 Hz, 8 Hz), 2.93 (1H, dd,J=15 Hz, 5 Hz), 3.43 (3H, s), 3.63 (1H, dd, J=10 Hz, 6 Hz), 3.71 (1H,dd, J=10 Hz, 5 Hz), 4.47-4.54 (1H, m), 6.78 (1H, dd, J=8 Hz, 5 Hz), 7.35(1H, brs), 7.56 (1H, dd, J=8 Hz, 1 Hz), 8.07 (1H, dd, J=5.1 Hz), 8.66(1H, brs).

(4) A mixture of 4.5 g of sodium hydrogen carbonate and 300 ml ofN,N-dimethylformamide was heated to 130° C., and thereto was addeddropwise a mixture of 7.48 g of the compound (22-1) and 100 ml ofN,N-dimethylformamide over 1 hour. The mixture was stirred at 130° C.for 1 hour. After the mixture was allowed to cool, water was addedthereto and the mixture was extracted with ethyl acetate. The organiclayer was washed sequentially with water and a saturated sodium chlorideaqueous solution, dried over sodium sulfate, and then concentrated underreduced pressure. A crystal formed was washed with a small amount ofethyl acetate to obtain 2.02 g of the compound (25-1).

¹H-NMR (CDCl₃, TMS) δ (ppm): 2.46 (1H, dd, J=17.1 Hz), 2.77 (1H, dd,J=17 Hz, 8 Hz), 3.41 (3H, s), 3.63 (1H, dd, J=10 Hz, 8 Hz), 3.82 (1H,dd, J=10 Hz, 5 Hz), 4.59-4.67 (1H, m), 7.02 (1H, dd, J=8 Hz, 5 Hz), 7.60(1H, s), 7.68 (1H, dd, J=8 Hz, 2 Hz), 8.20 (1H, dd, J=5 Hz, 2 Hz).

(5) To a mixture of 4.2 g of the compound (25-1), 20 ml of acetonitrileand 1 drop of N,N-dimethylformamide was added 6 g of phosphorusoxybromide at room temperature, and the mixture was heated under refluxfor 1 hour. After allowed to cool, the reaction mixture was poured intoice-water and extracted with ethyl acetate. The organic layer was washedwith water, dried over anhydrous magnesium sulfate, and thenconcentrated under reduced pressure. The resulting residue was subjectedto silica gel column chromatography to obtain 2.2 g of the compound(26-1).

¹H-NMR (CDCl₃, TMS) δ (ppm): 3.23 (2H, dd, J=10 Hz, 3 Hz), 3.34 (3H, s),3.48 (1H, dd, J=10 Hz, 6 Hz), 3.66 (1H, dd, J=10 Hz, 4 Hz), 5.01-5.13(1H, m), 6.91 (1H, dd, J=8 Hz, 5 Hz), 7.66 (1H, dd, J=8 Hz, 2 Hz), 8.17(1H, dd, J=5 Hz, 2 Hz).

(6) A mixture of 0.10 g of the compound (26-1), 3 ml of acetonitrile, acatalytic amount of copper sulfate and a drop of conc. sulfuric acid washeated to 80° C., and thereto was added dropwise a mixture of 0.14 g ofpotassium persulfate and 4 ml of water over 2 hours. The mixture wasstirred at 80° C. for 10 minutes. After the reaction mixture was allowedto cool, water was added thereto and the mixture was extracted withethyl acetate. The organic layer was washed with water, dried overanhydrous magnesium sulfate, and then concentrated under reducedpressure. The resulting residue was subjected to silica gel columnchromatography to obtain 0.06 g of the compound (17-1).

¹H-NMR (CDCl₃, TMS) δ (ppm): 3.23 (3H, s), 4.50 (2H, s), 6.47 (1H, s),7.39 (1H, dd, J=8 Hz, 5 Hz), 7.93 (1H, dd, J=8 Hz, 2 Hz), 8.47 (1H, dd,J=5 Hz, 2 Hz).

(7) A mixture of 0.30 g of the compound (17-1), 0.49 g of potassiumpersulfate, 1 ml of acetonitrile and 1 ml of water was stirred at 90° C.for 12 hours. After the reaction mixture was allowed to cool, water wasadded thereto and the mixture was extracted with ethyl acetate. Theorganic layer was washed with water, dried over anhydrous magnesiumsulfate, and then concentrated under reduced pressure. The resultingresidue was subjected to silica gel column chromatography to obtain 0.16g of the compound (2-1).

¹H-NMR (CDCl₃, TMS) δ (ppm): 7.11 (1H, s), 7.47 (1H, dd, J=8 Hz, 5 Hz),7.96 (1H, dd, J=8 Hz, 1 Hz), 8.52 (1H, dd, J=5 Hz, 1 Hz), 9.79 (1H, s).

Reference Production Example 9

(1) To a mixture of 4 g of 4-methoxycrotonic acid and a drop ofN,N-dimethylformamide was added dropwise 16.5 g of oxalyl chloride underice-cooling. The mixture was stirred at room temperature for 2 hours.The reaction mixture was concentrated under reduced pressure to obtain acrude product. All amount of the crude product obtained was used as itis for the following step.

4-Methoxycrotonoyl chloride

¹H-NMR (CDCl₃, TMS) δ (ppm): 3.43 (3H, s), 4.18 (2H, dd, J=4 Hz, 2 Hz),6.34 (1H, dt, J=15 Hz, 2 Hz), 7.19 (1H, dt, J=15 Hz, 4 Hz).

(2) To a mixture of crude product obtained in the above step (1), 50 mlof N,N-dimethyldormamide and 10 g of pyridine at room temperature wasadded 4.5 g of 3-chloro-2-hydrazinopyridine. The mixture was stirred for1 hour and then allowed to stand at room temperature overnight. Waterwas added to the reaction mixture, and the mixture was extracted withethyl acetate. The organic layer was washed with a saturated ammoniumchloride aqueous solution, dried over anhydrous magnesium sulfate, andthen concentrated under reduced pressure. A crude crystal formed waswashed with a small amount of ethyl acetate to obtain 2.3 g of thecompound (24-1).

¹H-NMR (CDCl₃, TMS) δ (ppm): 3.41 (3H, s), 4.10-4.15 (2H, m), 6.21 (1H,dt, J=15 Hz, 2 Hz), 6.76 (1H, dd, J=8 Hz, 5 Hz), 6.98 (1H, dt, J=15 Hz,4 Hz), 7.48-7.60 (2H, m), 8.07 (1H, dd, J=5 Hz, 1 Hz), 8.45 (1H, brs).

(3) A mixture of 8.0 g of the compound (24-1) and 24.0 g of acetonitrilewas cooled with a water bath, and hydrogen chloride gas was introducedthereinto under stirring. After the mixture was stirred while hydrogenchloride gas was introduced for about 3 hours, the reaction mixture wasconcentrated under reduced pressure. To the resulting residue was addeda saturated sodium bicarbonate aqueous solution, and the mixture wasextracted with ethyl acetate. The organic layer was washed with asaturated sodium chloride aqueous solution, dried over sodium sulfate,and then concentrated under reduced pressure to obtain 8.97 g of thecompound (22-1).

Reference Production Example 10

(1) To a mixture of 0.48 g of the compound (25-1) and 10 ml ofacetonitrile were added sequentially 0.25 g of methanesulfonyl chlorideand 0.30 g of triethylamine under ice-cooling. The mixture was stirredat 0° C. for 1 hour. Water was added to the reaction mixture, and themixture was extracted with ethyl acetate. The organic layer was washedwith water, dried over anhydrous magnesium sulfate, and thenconcentrated under reduced pressure. The resulting residue was subjectedto silica gel column chromatography to obtain 0.32 g of the compound(27-1).

¹H-NMR (CDCl₃, TMS) δ (ppm): 3.14 (2H, d, J=10 Hz), 3.36 (3H, s), 3.47(3H, s), 3.55 (1H, dd, J=10 Hz, 6 Hz), 3.66-3.74 (1H, m), 5.10-5.21 (1H,m), 6.87 (1H, dd, J=8 Hz, 5 Hz), 7.64 (1H, dt, J=8 Hz, 1 Hz), 8.14 (1H,dt, J=5 Hz, 1 Hz).

(2) A mixture of 0.53 g of the compound (27-1) and 1.2 g of a 33 wt %solution of hydrogen bromide in acetic acid was stirred at roomtemperature for 3 hours. The reaction mixture was poured into ice-water,and the mixture was extracted with ethyl acetate. The organic layer waswashed with a saturated sodium hydrogen carbonate aqueous solution,dried over anhydrous magnesium sulfate, and then concentrated underreduced pressure. The resulting residue was subjected to silica gelcolumn chromatography to obtain 0.30 g of the compound (26-1).

Then, specific examples of the compounds (1) are listed.

TABLE 2 Compound No. R¹ R² R³ R⁴ R⁵ 1-1  CH₃ CH₃ CH₃ Br Br 1-2  CH₃CH₂ HCH₃ Br Br 1-3  CH₃ H CH₃ CH₃ Cl 1-4  CH₃ H CH₃ Br Br 1-5  (CH₃)₂CH H CH₃Br Br 1-6  CH₃ CH₃ CH₃ CH₃ Cl 1-7  CH₃ H CH₃ CH₃ CN 1-8  CH₃ CH₃ CH₃ CH₃CN 1-9  CH₃ H CH₃ Cl Cl 1-10 CH₃ H CH₃CH₂ Cl Cl 1-11 CH₃ CH₃ CH₃ Cl Cl1-12 CH₃ CH₃ CH₃ Br Cl 1-13 CH₃CH₂ H CH₃ Cl Cl 1-14 CH₃(CH₂)₂ H CH₃ BrBr 1-15 CH₃ CH₃CH₂ CH₃ Br Br 1-16 CH₃CH₂ CH₃ CH₃ Br Br 1-17 CH₃CH₂CH₃CH₂ CH₃ Br Br 1-18 CH₃CH₂ H CH₃ CH₃ Cl 1-19 CH₃CH₂ H CH₃ CH₃ CN

Physical properties of some compounds (1) are shown.

Compound (1-1)

¹H-NMR (CDCl₃, TMS) δ (ppm): 3.11-3.18 (6H, m), 3.76 (3H, brs), 4.86(1.4H, brs), 5.23 (0.6H, brs), 7.17-7.25 (1H, m), 7.57 (1H, d, J=2 Hz).

Compound (1-2)

¹H-NMR (CDCl₃, TMS) δ (ppm): 1.21 (3H, t, J=7 Hz), 3.62 (2H, q, J=7 Hz),3.78 (3H, s), 4.95 (2H, brs), 6.96 (1H, brs), 7.26 (1H, d, J=2 Hz), 7.59(1H, d, J=2 Hz).

Compound (1-4)

¹H-NMR (CDCl₃, TMS) δ (ppm): 3.28 (3H, s), 3.76 (3H, s), 4.96 (2H, brs),7.00 (1H, brs), 7.27 (1H, d, J=2 Hz), 7.59 (1H, d, J=2 Hz).

Compound (1-15)

¹H-NMR (DMSO-d₆, 100° C., TMS) δ (ppm): 1.09 (3H, t, J=7 Hz), 3.12 (3H,s), 3.40-3.52 (2H, m), 3.70 (3H, s), 5.23 (2H, brs), 7.20 (1H, d, J=2Hz), 7.62 (1H, d, J=2 Hz).

Compound (1-16)

¹H-NMR (DMSO-d₆, 100° C., TMS) δ (ppm): 1.15 (3H, t, J=7 Hz), 3.07 (3H,s), 3.45-3.60 (2H, m), 3.67 (3H, s), 5.19 (2H, brs), 7.20 (1H, d, J=2Hz), 7.61 (1H, d, J=2 Hz).

Compound (1-17)

¹H-NMR (DMSO-d₆, 100° C., TMS) δ (ppm): 1.09-1.17 (6H, m), 3.40-3.55(4H, m), 3.69 (3H, s), 5.19 (2H, brs), 7.22 (1H, d, J=2 Hz), 7.62 (1H,d, J=2 Hz).

Then, specific examples of the compound (2) are listed below.

TABLE 3 Compound No. R⁶ R⁷ 2-1 Br Cl 2-2 CF₃ Cl 2-3 Cl Cl

Physical properties of some compounds (2) are shown.

Compound (2-1)

¹H-NMR (CDCl₃, TMS) δ (ppm): 7.11 (1H, s), 7.47 (1H, dd, J=8 Hz, 5 Hz),7.96 (1H, dd, J=8 Hz, 1 Hz), 8.52 (1H, dd, J=5 Hz, 1 Hz), 9.79 (1H, s).

Compound (2-2)

¹H-NMR (CDCl₃, TMS) δ (ppm): 7.36 (1H, s), 7.51 (1H, dd, J=8 Hz, 5 Hz),7.99 (1H, dd, J=8 Hz, 2 Hz), 8.54 (1H, dd, J=5 Hz, 2 Hz), 9.86 (1H, s).

Compound (2-3)

¹H-NMR (CDCl₃, TMS) δ (ppm): 7.02 (1H, s), 7.47 (1H, dd, J=8 Hz, 5 Hz),7.97 (1H, dd, J=8 Hz, 2 Hz), 8.51 (1H, dd, J=5 Hz, 2 Hz), 9.79 (1H, s).

Then, specific examples of the compound (17) are listed below.

TABLE 4 Compound No. R^(C) R⁶ R⁷ 17-1 CH₃ Br Cl 17-2 CH₃ Cl Cl

Physical properties of some compounds (17) are shown.

Compound (17-1)

¹H-NMR (CDCl₃, TMS) δ (ppm): 3.23 (3H, s), 4.50 (2H, s), 6.47 (1H, s),7.39 (1H, dd, J=8 Hz, 5 Hz), 7.93 (1H, dd, J=8 Hz, 2 Hz), 8.47 (1H, dd,J=5 Hz, 2 Hz).

Then, examples of formulation of the compound (3) as a pesticidalcomposition will be described as Reference Formulation Example.

Reference Formulation Example 1

A mixture of 10 parts of any one of the compounds (3-1) to (3-23),(3-25) to (3-27), (3-29) to (3-31) and (3-33), 35 parts of white carboncontaining 50 parts of polyoxyethylene alkyl ether sulfate ammoniumsalt, and 55 parts of water is finely ground by a wet grinding method toobtain a 10% flowable agent.

The following Reference Test Examples demonstrate that the compound (3)is useful as an active ingredient of a pesticidal composition.

Reference Test Example 1

Preparations of the compounds (3-1) to (3-23), (3-25) to (3-27), (3-29)to (3-31) and (3-33) obtained in Reference Formulation Example 1 werediluted with water so that the active ingredient concentration became500 ppm to prepare test spray solutions.

At the same time, a cabbage was planted in a polyethylene cup and grownuntil the third true leaf or the fourth true leaf was developed. Thetest spray solution as described above was sprayed in an amount of 20ml/cup on the cabbage.

After the drug solution sprayed on the cabbage was dried, the cabbagewas parasitized with 10 third-instar larvae of diamondback moths(Plutella xylostella) were put on the cabbage. After 5 days, the numberof diamondback moths was counted, and a controlling value was calculatedby the following equation:

Controlling value(%)={1−(Cb×Tai)/(Cai×Tb)}×100

wherein,

Cb: the number of worms in a non-treated section before treatment

Cai: the number of worms in a non-treated section on observation

Tb: the number of worms in a treated-section before treatment

Tai: the number of worms in a treated-section on observation.

As a result, the test spray solutions of the compounds (3-1) to (3-23),(3-25) to (3-27), (3-29) to (3-31) and (3-33) each exhibited acontrolling value of 80% or more.

Reference Test Example 2

Preparations of the compounds (3-1) to (3-23), (3-25) to (3-27), (3-29)to (3-31) and (3-33) obtained in Reference Formulation Example 1 wasdiluted with water so that the active ingredient concentration became500 ppm to prepare test spray solutions.

At the same time, a cucumber was planted in a polyethylene cup, and wasgrown until the first true leaf was developed. About 30 cotton aphids(Aphis gossypii) were put on the cucumber. One day after, the test spraysolution as described above was sprayed in an amount of 20 ml/cup on thecucumber. Six days after spraying, the number of cotton aphids wascounted, and a controlling value was calculated by the followingequation:

Controlling value(%)={1−(Cb×Tai)/(Cai×Tb)}×100

wherein,

Cb: the number of insects in a non-treated section before treatment

Cai: the number of insects in a non-treated section on observation

Tb: the number of insects in a treated-section before treatment

Tai: the number of insects in a treated-section on observation.

As a result, the test spray solutions of the compounds (3-1) to (3-23),(3-25) to (3-27), (3-29) to (3-31) and (3-33) each exhibited acontrolling value of 90% or more.

INDUSTRIAL APPLICABILITY

According to the present invention, the compound (3) having an excellentcontrolling activity on harmful arthropods can be produced.

1. An aldehyde compound represented by the formula (2):

wherein R⁶ represents a hydrogen atom, a halogen atom, a cyano group, aC1-C6 alkyl group optionally substituted with at least one halogen atom,a C1-C6 alkoxy group optionally substituted with at least one halogenatom, a C1-C6 alkylthio group optionally substituted with at least onehalogen atom, a C1-C6 alkylsulfinyl group optionally substituted with atleast one halogen atom, or a C1-C6 alkylsulfonyl group optionallysubstituted with at least one halogen atom, and R⁷ represents a halogenatom, or a C1-C6 alkyl group optionally substituted with at least onehalogen atom.
 2. The aldehyde compound according to claim 1, wherein R⁶represents a halogen atom or a C1-C6 alkyl group optionally substitutedwith at least one halogen atom.
 3. The aldehyde compound according toclaim 1, wherein R⁶ represents a halogen atom or a trifluoromethylgroup.
 4. The aldehyde compound according to claim 1, wherein R⁶represents a chlorine atom or a trifluoromethyl group, and R⁷ representsa chlorine atom.